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Photoluminescent coordination complexes of Cr(III) are of interest as near-infrared spin-flip emitters. Here, we explore the preparation, electrochemistry, and photophysical properties of the first two examples of homoleptic N-heterocyclic carbene complexes of Cr(III), featuring 2,6-bis(imidazolyl)pyridine (ImPyIm) and 2-imidazolylpyridine (ImPy) ligands. The complex [Cr(ImPy)3]3+ displays luminescence at 803 nm on the microsecond time scale (13.7 µs) from a spin-flip doublet excited state, which transient absorption spectroscopy reveals to be populated within several picoseconds following photoexcitation. Conversely, [Cr(ImPyIm)2]3+ is nonemissive and has a ca. 500 ps excited-state lifetime.
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Photochemical ligand release from metal complexes may be exploited in the development of novel photoactivated chemotherapy agents for the treatment of cancer and other diseases. Highly intriguing photochemical behavior is reported for two ruthenium(II) complexes bearing conformationally flexible 1,2,3-triazole-based ligands incorporating a methylene spacer to form 6-membered chelate rings. [Ru(bpy)2(pictz)]2+ (1) and [Ru(bpy)2(btzm)]2+ (2) (bpy = 2,2'-bipyridyl; pictz = 1-(picolyl)-4-phenyl-1,2,3-triazole; btzm = bis(4-phenyl-1,2,3-triazol-4-yl)methane) exhibit coordination by the triazole ring through the less basic N2 atom as a consequence of chelation and readily undergo photochemical release of the pictz and btzm ligands (Ï = 0.079 and 0.091, respectively) in acetonitrile solution to form cis-[Ru(bpy)2(NCMe)2]2+ (3) in both cases. Ligand-loss intermediates of the form [Ru(bpy)2(κ1-pictz or κ1-btzm)(NCCD3)]2+ are detected by 1H NMR spectroscopy and mass spectrometry. Photolysis of 1 yields three ligand-loss intermediates with monodentate pictz ligands, two of which form through simple decoordination of either the pyridine or triazole donor with subsequent solvent coordination (4-tz(N2) and 4-py, respectively). The third intermediate, shown to be able to form photochemically directly from 1, arises through linkage isomerism in which the monodentate pictz ligand is coordinated by the triazole N3 atom (4-tz(N3)) with a comparable ligand-loss intermediate with an N3-bound κ1-btzm ligand also observed for 2.
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A detailed understanding of the dynamics of photoinduced processes occurring in the electronic excited state is essential in informing the rational design of photoactive transition-metal complexes. Here, the rate of intersystem crossing in a Cr(III)-centered spin-flip emitter is directly determined through the use of ultrafast broadband fluorescence upconversion spectroscopy (FLUPS). In this contribution, we combine 1,2,3-triazole-based ligands with a Cr(III) center and report the solution-stable complex [Cr(btmp)2]3+ (btmp = 2,6-bis(4-phenyl-1,2,3-triazol-1-yl-methyl)pyridine) (13+), which displays near-infrared (NIR) luminescence at 760 nm (τ = 13.7 µs, Ï = 0.1%) in fluid solution. The excited-state properties of 13+ are probed in detail through a combination of ultrafast transient absorption (TA) and femtosecond-to-picosecond FLUPS. Although TA spectroscopy allows us to observe the evolution of phosphorescent excited states within the doublet manifold, more significantly and for the first time for a complex of Cr(III), we utilize FLUPS to capture the short-lived fluorescence from initially populated quartet excited states immediately prior to the intersystem crossing process. The decay of fluorescence from the low-lying 4MC state therefore allows us to assign a value of (823 fs)-1 to the rate of intersystem crossing. Importantly, the sensitivity of FLUPS to only luminescent states allows us to disentangle the rate of intersystem crossing from other closely associated excited-state events, something which has not been possible in the spectroscopic studies previously reported for luminescent Cr(III) systems.
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G-quadruplexes are emerging targets in cancer research and understanding how diagnostic probes bind to DNA G-quadruplexes in solution is critical to the development of new molecular tools. In this study the binding of an enantiopure NIR emitting [Os(TAP)2 (dppz)]2+ complex to different G-quadruplex structures formed by human telomer (hTel) and cMYC sequences in solution is reported. The combination of NMR and time-resolved infrared spectroscopic techniques reveals the sensitivity of the emission response to subtle changes in the binding environment of the complex. Similar behaviour is also observed for the related complex [Os(TAP)2 (dppp2)]2+ upon quadruplex binding.
Assuntos
Quadruplex G , Osmio , Humanos , DNA/química , Espectroscopia de Ressonância Magnética/métodos , Imageamento por Ressonância MagnéticaRESUMO
Ruthenium(II) complexes feature prominently in the development of agents for photoactivated chemotherapy; however, the excited-state mechanisms by which photochemical ligand release operates remain unclear. We report here a systematic experimental and computational study of a series of complexes [Ru(bpy)2(Nâ§N)]2+ (bpy = 2,2'-bipyridyl; Nâ§N = bpy (1), 6-methyl-2,2'-bipyridyl (2), 6,6'-dimethyl-2,2'-bipyridyl (3), 1-benzyl-4-(pyrid-2-yl)-1,2,3-triazole (4), 1-benzyl-4-(6-methylpyrid-2-yl)-1,2,3-triazole (5), 1,1'-dibenzyl-4,4'-bi-1,2,3-triazolyl (6)), in which we probe the contribution to the promotion of photochemical Nâ§N ligand release of the introduction of sterically encumbering methyl substituents and the electronic effect of replacement of pyridine by 1,2,3-triazole donors in the Nâ§N ligand. Complexes 2 to 6 all release the ligand Nâ§N on irradiation in acetonitrile solution to yield cis-[Ru(bpy)2(NCMe)2]2+, with resultant photorelease quantum yields that at first seem counter-intuitive and span a broad range. The data show that incorporation of a single sterically encumbering methyl substituent on the Nâ§N ligand (2 and 5) leads to a significantly enhanced rate of triplet metal-to-ligand charge-transfer (3MLCT) state deactivation but with little promotion of photoreactivity, whereas replacement of pyridine by triazole donors (4 and 6) leads to a similar rate of 3MLCT deactivation but with much greater photochemical reactivity. The data reported here, discussed in conjunction with previously reported data on related complexes, suggest that monomethylation in 2 and 5 sterically inhibits the formation of a 3MCcis state but promotes the population of 3MCtrans states which rapidly deactivate 3MLCT states and are prone to mediating ground-state recovery. On the other hand, increased photochemical reactivity in 4 and 6 seems to stem from the accessibility of 3MCcis states. The data provide important insights into the excited-state mechanism of photochemical ligand release by Ru(II) tris-bidentate complexes.
Assuntos
Compostos Organometálicos , Rutênio , Ligantes , Teoria Quântica , Compostos Organometálicos/química , Rutênio/química , TriazóisRESUMO
The synthesis and photophysical characterization of two osmium(II) polypyridyl complexes, [Os(TAP)2dppz]2+ (1) and [Os(TAP)2dppp2]2+ (2) containing dppz (dipyrido[3,2-a:2',3'-c]phenazine) and dppp2 (pyrido[2',3':5,6]pyrazino[2,3-f][1,10]phenanthroline) intercalating ligands and TAP (1,4,5,8-tetraazaphenanthrene) ancillary ligands, are reported. The complexes exhibit complex electrochemistry with five distinct reductive redox couples, the first of which is assigned to a TAP-based process. The complexes emit in the near-IR (1 at 761 nm and 2 at 740 nm) with lifetimes of >35 ns with a low quantum yield of luminescence in aqueous solution (â¼0.25%). The Δ and Λ enantiomers of 1 and 2 are found to bind to natural DNA and with AT and GC oligodeoxynucleotides with high affinities. In the presence of natural DNA, the visible absorption spectra are found to display significant hypochromic shifts, which is strongly evident for the ligand-centered π-π* dppp2 transition at 355 nm, which undergoes 46% hypochromism. The emission of both complexes increases upon DNA binding, which is observed to be sensitive to the Δ or Λ enantiomer and the DNA composition. A striking result is the sensitivity of Λ-2 to the presence of AT DNA, where a 6-fold enhancement of luminescence is observed and reflects the nature of the binding for the enantiomer and the protection from solution. Thermal denaturation studies show that both complexes are found to stabilize natural DNA. Finally, cellular studies show that the complexes are internalized by cultured mammalian cells and localize in the nucleus.
Assuntos
Substâncias Intercalantes , Rutênio , Animais , DNA/química , Substâncias Intercalantes/química , Ligantes , Mamíferos/metabolismo , Oligodesoxirribonucleotídeos , Osmio , Fenantrolinas/química , Fenazinas/química , Rutênio/químicaRESUMO
Diimine metal complexes have significant relevance in the development of photodynamic therapy (PDT) and photoactivated chemotherapy (PACT) applications. In particular, complexes of the TAP ligand (1,4,5,8-tetraazaphenanthrene) are known to lead to photoinduced oxidation of DNA, while TAP- and triazole-based complexes are also known to undergo photochemical ligand release processes relevant to PACT. The photophysical and photochemical properties of heteroleptic complexes [Ru(TAP)n(btz)3-n]2+ (btz = 1,1'-dibenzyl-4,4'-bi-1,2,3-triazolyl, n = 1 (1), 2 (2)) have been explored. Upon irradiation in acetonitrile, 1 displays analogous photochemistry to that previously observed for [Ru(bpy)(btz)2]2+ (bpy = 2,2'-bipyridyl) and generates trans-[Ru(TAP)(btz)(NCMe)2]2+ (5), which has been crystallographically characterized, with the observation of the ligand-loss intermediate trans-[Ru(TAP)(κ2-btz)(κ1-btz)(NCMe)]2+ (4). Complex 2 displays more complicated photochemical behavior with not only preferential photorelease of btz to form cis-[Ru(TAP)2(NCMe)2]2+ (6) but also competitive photorelease of TAP to form 5. Free TAP is then taken up by 6 to form [Ru(TAP)3]2+ (3) with the proportion of 5 and 3 observed to progressively increase during prolonged photolysis. Data suggest a complex set of reversible photochemical ligand scrambling processes in which 2 and 3 are interconverted. Computational DFT calculations have enabled optimization of geometries of the pro-trans 3MCcis states with repelled btz or TAP ligands crucial for the formation of 5 from 1 and 2, respectively, lending weight to recent evidence that such 3MCcis states play an important mechanistic role in the rich photoreactivity of Ru(II) diimine complexes.
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Fundamental insights into the mechanism of triplet-excited-state interligand energy transfer dynamics and the origin of dual emission for phosphorescent iridium(III) complexes are presented. The complexes [Ir(Câ§N)2(Nâ§N)]+ (HCâ§N = 2-phenylpyridine (1a-c), 2-(2,4-difluorophenyl)pyridine (2a-c), 1-benzyl-4-phenyl-1,2,3-triazole (3a-c); Nâ§N = 1-benzyl-4-(pyrid-2-yl)-1,2,3-triazole (pytz, a), 1-benzyl-4-(pyrimidin-2-yl)-1,2,3-triazole (pymtz, b), 1-benzyl-4-(pyrazin-2-yl)-1,2,3-triazole (pyztz, c)) are phosphorescent in room-temperature fluid solutions from triplet metal-to-ligand charge transfer (3MLCT) states admixed with either ligand-centered (3LC) (1a, 2a, and 2b) or ligand-to-ligand charge transfer (3LL'CT) character (1c, 2c, and 3a-c). Particularly striking is the observation that pyrimidine-based complex 1b exhibits dual emission from both 3MLCT/3LC and 3MLCT/3LL'CT states. At 77 K, the 3MLCT/3LL'CT component is lost from the photoluminescence spectra of 1b, with emission exclusively arising from its 3MLCT/3LC state, while for 2c switching from 3MLCT/3LL'CT- to 3MLCT/3LC-based emission is observed. Femtosecond transient absorption data reveal distinct spectral signatures characteristic of the population of 3MLCT/3LC states for 1a, 2a, and 2b which persist throughout the 3 ns time frame of the experiment. These 3MLCT/3LC state signatures are apparent in the transient absorption spectra for 1c and 2c immediately following photoexcitation but rapidly evolve to yield spectral profiles characteristic of their 3MLCT/3LL'CT states. Transient data for 1b reveals intermediate behavior: the spectral features of the initially populated 3MLCT/3LC state also undergo rapid evolution, although to a lesser extent than that observed for 1c and 2c, behavior assigned to the equilibration of the 3MLCT/3LC and 3MLCT/3LL'CT states. Density functional theory (DFT) calculations enabled minima to be optimized for both 3MLCT/3LC and 3MLCT/3LL'CT states of 1a-c and 2a-c. Indeed, two distinct 3MLCT/3LC minima were optimized for 1a, 1b, 2a, and 2b distinguished by upon which of the two Câ§N ligands the excited electron resides. The 3MLCT/3LC and 3MLCT/3LL'CT states for 1b are very close in energy, in excellent agreement with experimental data demonstrating dual emission. Calculated vibrationally resolved emission spectra (VRES) for the complexes are in excellent agreement with experimental data, with the overlay of spectral maxima arising from emission from the 3MLCT/3LC and 3MLCT/3LL'CT states of 1b convincingly reproducing the observed experimental spectral features. Analysis of the optimized excited-state geometries enable the key structural differences between the 3MLCT/3LC and 3MLCT/3LL'CT states of the complexes to be identified and quantified. The calculation of interconversion pathways between triplet excited states provides for the first time a through-space mechanism for a photoinduced interligand energy transfer process. Furthermore, examination of structural changes between the possible emitting triplet excited states reveals the key bond vibrations that mediate energy transfer between these states. This work therefore provides for the first time detailed mechanistic insights into the fundamental photophysical processes of this important class of complexes.
RESUMO
In a systematic survey of luminescent bis(terdentate) osmium(II) complexes, a tipping point involving a reversal in photophysical tuning is observed whereby increasing stabilization of the ligand-based lowest unoccupied molecular orbital (LUMO) results in a blue shift in the optical absorption and emission bands. The complexes [Os(N^N'^Nâ³)2]2+ [N^N'^Nâ³ = 2,6-bis(1-phenyl-1,2,3-triazol-4-yl)pyridine (Os1), 2,6-bis(1-benzyl-1,2,3-triazol-4-yl)pyrazine (Os2), 6-(1-benzyl-1,2,3-triazol-4-yl)-2,2'-bipyridyl (Os3), 2-(pyrid-2-yl)-6-(1-benzyl-1,2,3-triazol-4-yl)pyrazine (Os4), 2-(pyrazin-2-yl)-6-(1-benzyl-1,2,3-triazol-4-yl)pyridine (Os5), and 6-(1-benzyl-1,2,3-triazol-4-yl)-2,2'-bipyrazinyl (Os6)] have been prepared and characterized, and all complexes display phosphorescence ranging from the orange to near-IR regions of the spectrum. Replacement of the central pyridine in the ligands of Os1 by the more π-accepting pyrazine in Os2 results in a 55 nm red shift in the triplet metal-to-ligand charge-transfer-based emission band, while a larger red shift of 107 nm is observed for the replacement of one of the triazole donors in the ligands of Os1 by a second pyridine ring in Os3 (λemmax = 702 nm). Interestingly, replacement of the central pyridine ring in the ligands of Os3 by pyrazine (Os4, λemmax = 702 nm) fails to result in a further red shift in the emission band. Reversal of the relative positions of the pyridine and pyrazine donors in Os5 (λemmax = 733 nm) compared to Os4 does indeed result in the expected red shift in the emission with respect to that for Os3 based on the increased π-acceptor character of the ligands present. However, an inversion in emission tuning is observed for Os6, in which the incorporation of a second pyrazine donor in the ligand architecture results in a blue shift in the optical absorption and emission maxima (λemmax = 710 nm). Electrochemical studies reveal that while incorporating pyrazine in the ligands indeed results in an expected anodic shift in the first reduction potential through stabilization of the ligand-based LUMO, there is also a concomitant anodic shift in the OsII/OsIII-based oxidation potential. This stabilization of the metal-based highest occupied molecular orbital (HOMO) thus nullifies the effect of stabilization of the LUMO in Os4 compared to Os3, resulting in these complexes having coincident emission maxima. For Os6, stabilization of the HOMO through the incorporation of two pyrazine donors in the ligand structure now exceeds stabilization of the LUMO, resulting in a larger HOMO-LUMO gap and a counterintuitive blue shift in the optical properties in comparison with those of Os5. While it is known that the replacement of ligands (e.g., replacing bipyridyl with bipyrazinyl) can result in a larger HOMO-LUMO energy gap through greater stabilization of the HOMO, these results importantly allow us to capture the tipping point at which this inversion in photophysical tuning occurs. This therefore enables us to explore the limits available in emission tuning with a relatively simple and minimalist ligand structure.
RESUMO
The series of complexes [Os(bpy)3- n(pytz) n][PF6]2 (bpy = 2,2'-bipyridyl, pytz = 1-benzyl-4-(pyrid-2-yl)-1,2,3-triazole, 1 n = 0, 2 n = 1, 3 n = 2, 4 n = 3) were prepared and characterized and are rare examples of luminescent 1,2,3-triazole-based osmium(II) complexes. For 3 we present an attractive and particularly mild preparative route via an osmium(II) η6-arene precursor circumventing the harsh conditions that are usually required. Because of the high spin-orbit coupling constant associated with the Os(II) center the absorption spectra of the complexes all display absorption bands of appreciable intensity in the range of 500-700 nm corresponding to spin-forbidden ground-state-to-3MLCT transitions (MLCT = metal-to-ligand charge transfer), which occur at significantly lower energies than the corresponding spin-allowed 1MLCT transitions. The homoleptic complex 4 is a bright emitter (λmaxem = 614 nm) with a relatively high quantum yield of emission of â¼40% in deoxygenated acetonitrile solutions at room temperature. Water-soluble chloride salts of 1-4 were also prepared, all of which remain emissive in aerated aqueous solutions at room temperature. The complexes were investigated for their potential as phosphorescent cellular imaging agents, whereby efficient excitation into the 3MLCT absorption bands at the red side of the visible range circumvents autofluorescence from biological specimens, which do not absorb in this region of the spectrum. Confocal microscopy reveals 4 to be readily taken up by cancer cell lines (HeLa and EJ) with apparent lysosomal and endosomal localization, while toxicity assays reveal that the compounds have low dark and light toxicity. These complexes therefore provide an excellent platform for the development of efficient luminescent cellular imaging agents with advantageous photophysical properties that enable excitation and emission in the biologically transparent region of the optical spectrum.
Assuntos
Complexos de Coordenação/química , Substâncias Luminescentes/química , Imagem Óptica , Osmio/química , Piridinas/química , Triazóis/química , Sobrevivência Celular/efeitos dos fármacos , Complexos de Coordenação/síntese química , Complexos de Coordenação/farmacologia , Células HeLa , Humanos , Substâncias Luminescentes/síntese química , Substâncias Luminescentes/farmacologia , Medições Luminescentes , Estrutura Molecular , Processos Fotoquímicos , Teoria Quântica , Células Tumorais CultivadasRESUMO
We report the synthesis, characterization, and photochemical reactivity of the triazole-containing complex [Ru(pytz)(btz)2](2+) (1, pytz = 1-benzyl-4-(pyrid-2-yl)-1,2,3-triazole, btz = 1,1'-dibenzyl-4,4'-bi-1,2,3-triazolyl). The UV-vis absorption spectrum of 1 exhibits pytz- and btz-centered (1)MLCT bands at 365 and 300 nm, respectively. Upon photoexcitation, acetonitrile solutions of 1 undergo conversion to the ligand-loss intermediate, trans-[Ru(pytz)(κ(2)-btz)(κ(1)-btz)(NCMe)](2+) (2, Φ363 = 0.013) and ultimately to the ligand-loss product trans-[Ru(pytz)(btz)(NCMe)2](2+) (3), both of which are observed and characterized by (1)H NMR spectroscopy. Time-dependent density functional theory calculations reveal that the S1 state of the complex has primarily HOMO â LUMO pytz-based (1)MLCT character. Data show that the (3)MLCT and (3)MC states are in close energetic proximity (≤0.11 eV to 2 d.p.) and that the T1 state from a single-point triplet state calculation at the S0 geometry suggests (3)MC character. Optimization of the T1 state of the complex starting from the ground state geometry leads to elongation of the two Ru-N(btz) bonds cis to the pytz ligand to 2.539 and 2.544 Å leading to a pseudo-4-coordinate (3)MC state rather than the (3)MLCT state. The work therefore provides additional insights into the photophysical and photochemical properties of ruthenium triazole-containing complexes and their excited state dynamics.
RESUMO
The complex [Os(btzpy)2][PF6]2 (1, btzpy = 2,6-bis(1-phenyl-1,2,3-triazol-4-yl)pyridine) has been prepared and characterised. Complex 1 exhibits phosphorescence (λem = 595 nm, τ = 937 ns, φem = 9.3% in degassed acetonitrile) in contrast to its known ruthenium(II) analogue, which is non-emissive at room temperature. The complex undergoes significant oxygen-dependent quenching of emission with a 43-fold reduction in luminescence intensity between degassed and aerated acetonitrile solutions, indicating its potential to act as a singlet oxygen sensitiser. Complex 1 underwent counterion metathesis to yield [Os(btzpy)2]Cl2 (1Cl), which shows near identical optical absorption and emission spectra to those of 1. Direct measurement of the yield of singlet oxygen sensitised by 1Cl was carried out (φ (¹O2) = 57%) for air equilibrated acetonitrile solutions. On the basis of these photophysical properties, preliminary cellular uptake and luminescence microscopy imaging studies were conducted. Complex 1Cl readily entered the cancer cell lines HeLa and U2OS with mitochondrial staining seen and intense emission allowing for imaging at concentrations as low as 1 µM. Long-term toxicity results indicate low toxicity in HeLa cells with LD50 >100 µM. Osmium(II) complexes based on 1 therefore present an excellent platform for the development of novel theranostic agents for anticancer activity.
Assuntos
Mitocôndrias/ultraestrutura , Compostos Organometálicos/síntese química , Compostos Organometálicos/farmacologia , Osmio/química , Triazóis/síntese química , Triazóis/farmacologia , Linhagem Celular Tumoral , Sobrevivência Celular/efeitos dos fármacos , Células HeLa , Humanos , Medições Luminescentes , Mitocôndrias/efeitos dos fármacos , Mitocôndrias/metabolismo , Modelos Moleculares , Estrutura Molecular , Compostos Organometálicos/química , Oxigênio Singlete/química , Solubilidade , Nanomedicina Teranóstica , Triazóis/química , Água/químicaRESUMO
Whilst [Os(N^N)3 ](2+) complexes are supposed to be photochemically inert to ligand loss, the complex [Os(btz)3 ](2+) (btz=1,1'-dibenzyl-4,4'-bi-1,2,3-triazolyl) undergoes unprecedented photolytic reactivity to liberate free btz (Φ363 ≈1.2 %). Further, both cis and trans isomers of the photodechelated ligand-loss solvento intermediate [Os(κ(2) -btz)2 (κ(1) -btz)(NCMe)](2+) are unambiguously observed and characterized by NMR spectroscopy and mass spectrometry.
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Thanks to major advances in laser technologies, recent investigations of the ultrafast coupling of nuclear and electronic degrees of freedom (vibronic coupling) have revealed that such coupling plays a crucial role in a wide range of photoinduced reactions in condensed phase supramolecular systems. This paper investigates several new donor-bridge-acceptor charge-transfer molecular assemblies built on a trans-Pt(II) acetylide core. We also investigate how targeted vibrational excitation with low-energy IR light post electronic excitation can perturb vibronic coupling and affect the efficiency of electron transfer (ET) in solution phase. We compare and contrast properties of a range of donor-bridge-acceptor Pt(II) trans-acetylide assemblies, where IR excitation of bridge vibrations during UV-initiated charge separation in some cases alters the yields of light-induced product states. We show that branching to multiple product states from a transition state with appropriate energetics is the most rigid condition for the type of vibronic control we demonstrate in our study.
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Visible light-induced charge transfer dynamics were investigated in a novel transition metal triad acceptor-chromophore-donor, (NDI-phen)Pt(II)(-C≡C-Ph-CH2-PTZ)2 (1), designed for photoinduced charge separation using a combination of time-resolved infrared (TRIR) and femtosecond electronic transient absorption (TA) spectroscopy. In 1, the electron acceptor is 1,4,5,8-naphthalene diimide (NDI), and the electron donor is phenothiazine (PTZ), and [(phen)Pt(-C≡C-Ph-)], where phen is 1,10-phenanthroline, represents the chromophoric core. The first excited state observed in 1 is a (3)MLCT/LL'CT, with {Pt(II)-acetylide}-to-phen character. Following that, charge transfer from the phen-anion onto the NDI subunit to form NDI(-)-phen-[Pt-(C≡C)2](+)-PTZ2 occurs with a time constant of 2.3 ps. This transition is characterised by appearance of the prominent NDI-anion features in both TRIR and TA spectra. The final step of the charge separation in 1 proceeds with a time constant of â¼15 ps during which the hole migrates from the [Pt-(C≡C)2] subunit to one of the PTZ groups. Charge recombination in 1 then occurs with two distinct time constants of 36 ns and 107 ns, corresponding to the back electron transfer to each of the two donor groups; a rather rare occurrence which manifests that the hole in the final charge-separated state is localised on one of the two donor PTZ groups. The assignment of the nature of the excited states and dynamics in 1 was assisted by TRIR investigations of the analogous previously reported ((COOEt)2bpy)Pt(C≡C-Ph-CH2-PTZ)2 (2), (J. E. McGarrah and R. Eisenberg, Inorg. Chem., 2003, 42, 4355; J. E. McGarrah, J. T. Hupp and S. N. Smirnov, J. Phys. Chem. A, 2009, 113, 6430) as well as (bpy)Pt(C≡C-Ph-C7H15)2, which represent the acceptor-free dyad, and the chromophoric core, respectively. Thus, the step-wise formation of the full charge-separated state on the picosecond time scale and charge recombination via tunnelling have been established; and the presence of two distinct charge recombination pathways has been observed.
Assuntos
Elétrons , Naftalimidas/química , Compostos Organoplatínicos/química , Fenotiazinas/química , Platina/química , Transporte de Elétrons , Luz , Estrutura Molecular , Compostos Organoplatínicos/síntese química , Processos Fotoquímicos , Teoria QuânticaRESUMO
The compounds M2(TiPB)3(HDON) (TiPB = 2,4,6-triisopropylbenzoic acid; H2DON = 2,7-dihdroxy-1,8-napthyridine; M = Mo (1a) or W (1b)) and Mo2(TiPB)2(O2CCH2Cl)(HDON) (1c) which contain a pendant 2-pyridone functional group have been prepared. These compounds are capable of forming self-complementary hydrogen bonds, resulting in the formation of "dimers of dimers" ([1a-c]2) in CH2Cl2 solutions. Electrochemical studies reveal two successive one-electron redox processes for [1a-c]2 in CH2Cl2 solutions that correspond to successive oxidations of the dimetal core, indicating stabilization of the mixed-valence state. Only small changes in the value of Kc are observed upon changing the ancillary ligand or metal, implying that proton coupled mixed valency is responsible for the stabilization. Dimethylsulfoxide (DMSO) disrupts the hydrogen bonding interactions in these compounds, and a single oxidation process is observed in DMSO which shifts to lower potential as the number of HDON ligands increases. Further substitution of carboxylate ligands with HDON leads to the formation of Mo2(TiPB)2(HDON)2 (2) and Mo2(HDON)4 (3), which adopt trans-1,1 and cis-2,2 regioisomers in the solid-state. (1)H NMR spectroscopy indicates that there are at least two regioisomers present in solution for both compounds. The lowest energy transition in the electronic absorption spectra of these compounds corresponds to a M2-δ â HDON-π* transition. The electrochemical, spectroscopic and structural results were rationalized with the aid of density functional theory (DFT) calculations.
Assuntos
Molibdênio/química , Compostos Organometálicos/química , Piridonas/química , Tungstênio/química , Transporte de Elétrons , Ligação de Hidrogênio , Modelos Moleculares , Estrutura Molecular , Compostos Organometálicos/síntese química , Teoria QuânticaRESUMO
To unravel the role of driving force and structural changes in directing the photoinduced pathways in donor-bridge-acceptor (DBA) systems, we compared the ultrafast dynamics in novel DBAs which share a phenothiazine (PTZ) electron donor and a Pt(ii) trans-acetylide bridge (-C[triple bond, length as m-dash]C-Pt-C[triple bond, length as m-dash]C-), but bear different acceptors conjugated into the bridge (naphthalene-diimide, NDI; or naphthalene-monoimide, NAP). The excited state dynamics were elucidated by transient absorption, time-resolved infrared (TRIR, directly following electron density changes on the bridge/acceptor), and broadband fluorescence-upconversion (FLUP, directly following sub-picosecond intersystem crossing) spectroscopies, supported by TDDFT calculations. Direct conjugation of a strong acceptor into the bridge leads to switching of the lowest excited state from the intraligand 3IL state to the desired charge-separated 3CSS state. We observe two surprising effects of an increased strength of the acceptor in NDI vs. NAP: a ca. 70-fold slow-down of the 3CSS formation-(971 ps)-1vs. (14 ps)-1, and a longer lifetime of the 3CSS (5.9 vs. 1 ns); these are attributed to differences in the driving force ΔGet, and to distance dependence. The 100-fold increase in the rate of intersystem crossing-to sub-500 fs-by the stronger acceptor highlights the role of delocalisation across the heavy-atom containing bridge in this process. The close proximity of several excited states allows one to control the yield of 3CSS from â¼100% to 0% by solvent polarity. The new DBAs offer a versatile platform for investigating the role of bridge vibrations as a tool to control excited state dynamics.
RESUMO
The tris(1,2,3-triazol-4-yl)methane framework offers a highly versatile architecture for ligand design, yet the coordination chemistry of this class of ligand remains largely unexplored. We report here the synthesis and characterisation of the homoleptic complexes [M(ttzm)2](PF6)2 (ttzm = tris(1-benzyl-1,2,3-triazol-4-yl)-p-anisolylmethane; M = Fe (Fe), Ru (Ru), Os (Os)). Initial attempts to prepare Ru by reaction of [Ru(p-cymene)Cl2]2 and ttzm also led to the isolation of the heteroleptic complex [Ru(p-cymene)(ttzm)](PF6)2. The structures of [Ru(p-cymene)(ttzm)](PF6)2, [Fe(ttzm)2]2+ (as its BPh4- salt) and Os were solved by X-ray diffraction. The homoleptic Fe(II) and Os(II) containing cations adopt distorted octahedral geometries due to the steric interactions between the ansiole and triazole rings of the ttzm ligands. The homoleptic complexes all adopt a low-spin d6 configuration and exhibit reversible M(II)/M(III) processes (+0.35 to +0.72 V vs. Fc/Fc+). These oxidation processes are cathodically shifted relative to those of related hexatriazole donor based complexes with density functional theory (DFT) calculations showing the metal d-orbitals are destabilised through a π-donor contribution from the triazole rings. The complexes all show prominent UV-visible absorption bands between 350 and 450 nm assigned to transitions of 1MLCT character. Whilst none of the homoleptic complexes are emissive in room temperature fluid solutions, Os is emissive at 77 K in an EtOH/MeOH glass (λmax 472 nm).
RESUMO
Re(i) complexes bearing thermally reversible photochromic naphthopyran axial ligands undergo highly efficient, reversible phosphorescence quenching actuated by either visible or UV irradiation. The photoinduced quenching of the triplet metal-to-ligand charge-transfer (3MLCT) emission is interpreted based on changes in the relative energies of the excited states.
RESUMO
Cellular uptake, luminescence imaging and antimicrobial activity against clinically relevant methicillin-resistant S. aureus (MRSA) bacteria are reported. The osmium(ii) complexes [Os(N^N)3]2+ (N^N = 1-benzyl-4-(pyrid-2-yl)-1,2,3-triazole (1 2+); 1-benzyl-4-(pyrimidin-2-yl)-1,2,3-triazole (2 2+); 1-benzyl-4-(pyrazin-2-yl)-1,2,3-triazole (3 2+)) were prepared and isolated as the chloride salts of their meridional and facial isomers. The complexes display prominent spin-forbidden ground state to triplet metal-to-ligand charge transfer (3MLCT) state absorption bands enabling excitation as low as 600 nm for fac/mer-3 2+ and observation of emission in aqueous solution in the deep-red/near-IR regions of the spectrum. Cellular uptake studies within MRSA cells show antimicrobial activity for 1 2+ and 2 2+ with greater toxicity for the meridional isomers in each case and mer-1 2+ showing the greatest potency (32 µg mL-1 in defined minimal media). Super-resolution imaging experiments demonstrate binding of mer- and fac-1 2+ to bacterial DNA with high Pearson's colocalisation coefficients (up to 0.95 using DAPI). Phototoxicity studies showed the complexes exhibited a higher antimicrobial activity upon irradiation with light.