Excited-State Bond Contraction and Charge Migration in a Platinum Dimer Complex Characterized by X-ray and Optical Transient Absorption Spectroscopy.

Interactions between metal centers in dimeric transition metal complexes (TMCs) play important roles in their excited-state energetics and pathways and, thus, affect their photophysical properties relevant to their applications, for example, photoluminescent materials and photocatalysis. Here, we report electronic and nuclear structural dynamics studies of two photoexcited pyrazolate-bridged [Pt(ppy)(µ-R2pz)]2-type Pt(II) dimers (ppy = 2-phenylpyridine, µ-R2pz = 3,5-substituted pyrazolate): [Pt(ppy)(µ-H2pz)]2 (1) and [Pt(NDI-ppy)(µ-Ph2pz)]2 (2, NDI = 1,4,5,8-naphthalenediimide), both of which have distinct ground-state Pt-Pt distances. X-ray transient absorption (XTA) spectroscopy at the Pt LIII-edge revealed a new d-orbital vacancy due to the one-electron oxidation of the Pt centers in 1 and 2. However, while a transient Pt-Pt contraction was observed in 2, such an effect was completely absent in 1, demonstrating how the excited states of these complexes are determined by the overlap of the Pt (dz2) orbitals, which is tuned by the steric bulk of the pyrazolate R-groups in the 3- and 5-positions. In tandem with analysis of the Pt-Pt distance structural parameter, we observed photoinduced electron transfer in 2 featuring a covalently linked NDI acceptor on the ppy ligand. The formation and subsequent decay of the NDI radical anion absorption signals were detected upon photoexcitation using optical transient absorption spectroscopy. The NDI radical anion decayed on the same time scale, hundreds of picoseconds, as that of the d-orbital vacancy signal of the oxidized Pt-Pt core observed in the XTA measurements. The data indicated an ultrafast formation of the charge-separated state and subsequent charge recombination to the original Pt(II-II) species.

Probing Interligand Electron Transfer in the 1MLCT S1 Excited State of trans-Mo2L2L'2 Compounds: A Comparative Study of Auxiliary Ligands and Solvents.

The interligand charge dynamics of the lowest singlet metal-to-ligand charge-transfer states (1MLCT S1 states) of a series of quadruply bonded trans-Mo2(NN)2(O2C-X)2 paddlewheel compounds are investigated, where NN is a π-accepting phenylpropiolamidinate ligand and O2C-X (X = Me, tBu, TiPB, or CF3) is an auxiliary carboxylate ligand. The compounds show strong light absorption in the visible region due to MLCT transitions from the Mo2 center to the NN ligands. The transferred electron density was followed by femtosecond time-resolved infrared (fs-TRIR) spectroscopy with vibrational reporters such as the ethynyl groups on the NN ligands. The observed fs-TRIR spectra show that these compounds have asymmetric 1MLCT S1 excited states where the transferred electron mainly resides on a single NN ligand. The presence of interligand electron transfer (ILET) is suggested to explain the shape of the ν(C≡C) bands and the influence of auxiliary ligands and solvents on the interligand electronic coupling. The ILET in the 1MLCT S1 state is shown to be sensitive to the functional groups on the auxiliary ligands while being less responsive to changes in solvents.

Probing the solvation structure and dynamics in ionic liquids by time-resolved infrared spectroscopy of 4-(dimethylamino)benzonitrile.

In this work we demonstrate the use of the push-pull model system 4-(dimethylamino)benzonitrile (DMABN) as a convenient molecular probe to investigate the local solvation structure and dynamics by means of time-resolved infrared spectroscopy (TRIR). The photochemical features associated with this system provide several advantages due to the high charge separation between the ground and charge transfer states involving the characteristic nitrile bond, and an excited state lifetime that is long enough to observe the slow solvation dynamics in organic solvents and ionic liquids. The conversion from a locally excited state to an intramolecular charge transfer state (LE-ICT) in ionic liquids shows similar kinetic lifetimes in comparison to organic solvents. This similarity confirms that such conversion depends solely on the intramolecular reorganization of DMABN in the excited state, and not by the dynamics of solvation. In contrast, the relative shift of the ν(CN) vibration during the relaxation of the ICT state reveals two distinct lifetimes that are sensitive to the solvent environment. This study reveals a fast time component which is attributed to the dipolar relaxation of the solvent and a slower time component related to the rotation of the dimethylamino group of DMABN.

Can Excited State Electronic Coherence Be Tuned via Molecular Structural Modification? A First-Principles Quantum Electronic Dynamics Study of Pyrazolate-Bridged Pt(II) Dimers.

Materials and molecular systems exhibiting long-lived electronic coherence can facilitate coherent transport, opening the door to efficient charge and energy transport beyond traditional methods. Recently, signatures of a possible coherent, recurrent electronic motion were identified in femtosecond pump-probe spectroscopy experiments on a binuclear platinum complex, where a persistent periodic beating in the transient absorption signal's anisotropy was observed. In this study, we investigate the excitonic dynamics that underlie the suspected electronic coherence for a series of binuclear platinum complexes exhibiting a range of interplatinum distances. Results suggest that the long-lived coherence can only result when competitive electronic couplings are in balance. At longer Pt-Pt distances, the electronic couplings between the two halves of the binuclear system weaken, and exciton localization and recombination is favored on short time scales. For short Pt-Pt distances, electronic couplings between the states in the coherent superposition are stronger than the coupling with other excitonic states, leading to long-lived coherence.

Photophysical studies of metal to ligand charge transfer involving quadruply bonded complexes of molybdenum and tungsten.

Photoinduced metal-to-ligand charge transfer transitions afford numerous applications in terms of photon energy harvesting. The majority of metal complexes studied to date involve diamagnetic systems of d(6), d(8), and d(10) transition metals. These typically have very short-lived, ∼100 fs, singlet metal to ligand charge transfer ((1)MLCT) states that undergo intersystem crossing to triplet metal to ligand charge transfer ((3)MLCT) states that are longer lived and are responsible for much of the photophysical studies. In contrast, the metal-metal quadruply bonded complexes of molybdenum and tungsten supported by carboxylate, O2CR, and related amidinate ligands (RN)2C(R') have relatively long-lived (1)MLCT states arising from M2δ to Lπ* transitions. These have lifetimes in the range 1-20 ps prior to intersystem crossing to T1 states that may be (3)MLCT or (3)MMδδ* with lifetimes of 1-100 ns and 1-100 µs, respectively. The M2 quadruply bonded complexes take the form M2L4 or M2L4-nL'n where n = 1-3. Thus, in their photoexcited MLCT states, these compounds pose the question of how the charge resides on the ligands. This Account reviews the current knowledge of how charge is positioned with time in S1 and T1 states with the aid of active IR reported groups located on the ligands, for example, C≡X multiple bonds (X = C, N, or O). Several examples of localized and delocalized charge distributions are noted along with kinetic barriers to the interconversion of MLCT and δδ* states. On the 50th anniversary of the recognition of the MM quadruple bond, these complexes are revealing some remarkable features in the study of the photophysical properties of metal-ligand charge transfer states.

Tunable Excited-State Properties and Dynamics as a Function of Pt-Pt Distance in Pyrazolate-Bridged Pt(II) Dimers.

The influence of molecular structure on excited-state properties and dynamics of a series of cyclometalated platinum dimers was investigated through a combined experimental and theoretical approach using femtosecond transient absorption (fs TA) spectroscopy and density functional theory (DFT) calculations. The molecules have the general formula [Pt(ppy)(µ-R2pz)]2, where ppy = 2-phenylpyridine, pz = pyrazolate, and R = H, Me, Ph, or (t)Bu, and are strongly photoluminescent at room temperature. The distance between the platinum centers in this A-frame geometry can be varied depending on the steric bulk of the bridging pyrazolate ligands that exert structural constraints and compress the Pt-Pt distance. At large Pt-Pt distances there is little interaction between the subunits, and the chromophore behaves similar to a monomer with excited states described as mixtures of ligand-centered and metal-to-ligand charge transfer (LC/MLCT) transitions. When the Pt(II) centers are brought closer together with bulky bridging ligands, they interact through their dz(2) orbitals and the S1 and T1 states are best characterized as metal-metal-to-ligand charge transfer (MMLCT) in character. The results of the femtoseconds TA experiments reveal that intersystem crossing (ISC) occurs on ultrafast time scales (τS1 < 200 fs), while there are two relaxation processes occurring within the triplet manifold, τ1 = 0.5-3.2 ps and τ2 = 20-70 ps; the longer time constants correspond to the presence of bulkier bridging ligands. DFT calculations illustrate that the Pt-Pt distances further contract in the T1 (3)MMLCT states; therefore, slower relaxation may be related to a larger structural reorganization. Subsequent investigations using faster time resolution are planned to measure the ISC process as well as to identify any potential coherent interaction(s) between the platinum centers that may occur.

Photophysical properties of cis-Mo2 quadruply bonded complexes and observation of photoinduced electron transfer to titanium dioxide.

The compounds cis-Mo2(DAniF)2(L)2 have been prepared, where DAniF = (N,N')-p-dianisyl formamidinate and L = thienyl-2-carboxylate (Th), 2,2'-bithienyl-5-carboxylate (BTh), and 2,2':5',5″-terthienyl-5-carboxylate (TTh). The compounds have been characterized by proton nuclear magnetic resonance ((1)H NMR), ultraviolet-visible (UV-vis) absorption and emission, differential pulse voltammetry, and time-resolved transient absorption and infrared (IR) spectroscopy. An X-ray crystal structure was obtained for the thienyl complex. The related salt [(n)Bu4N]2[Mo2(DAniF)2(TTh-CO2)2], where TTh-CO2 = 2,2':5',2″-terthienyl-5,5″-dicarboxylate, has also been prepared and employed in the attachment of the complex to TiO2 nanoparticles. The latter have been characterized by ground-state Fourier transform infrared spectroscopy (FTIR) and femtosecond time-resolved IR spectroscopy. The time-resolved data provide evidence for sub-picosecond charge injection from the Mo2 center to the semiconducting oxide particle.

Mo2 paddlewheel complexes functionalized with a single MLCT, S1 infrared-active carboxylate reporter ligand: preparation and studies of ground and photoexcited states.

From the reactions between Mo2(DAniF)3pivalate (DAniF = N,N'-di(p-anisyl)formamidinate) and the carboxylic acids LH, the title compounds Mo2(DAniF)3L have been prepared and characterized: compounds I (L = O2CC≡CPh), II (L = O2CC4H2SC≡CH), and III (L = O2CC6H4-p-CN). The new compounds have been characterized in their ground states by spectroscopy ((1)H NMR, ultraviolet-visible absorption, near-infrared absorption, and steady state emission), cyclic voltammetry, and density functional theory calculations. The compounds show strong metal Mo2 to ligand L δ-π* transitions in their visible spectra. The nature of the S1 (1)MLCT and T1 states has been probed by time-resolved (femtosecond and nanosecond) transient absorption and infrared spectroscopy. The observed shifts of the C≡C and C≡N vibrational modes are found to be consistent with the negative charge being localized on the single L in the S1 states, while the T1 states are (3)Mo2 δδ*. The present results are compared to earlier studies of the photoexcited states of trans-Mo2(2,4,6-triisopropylbenzoate)2L2 compounds that have been assigned as either localized or delocalized.

Metal-metal quadruple bonds supported by 5-ethynylthiophene-2-carboxylato ligands: preparation, molecular and electronic structures, photoexcited state dynamics, and application as molecular synthons.

From the reaction between M2(T(i)PB)4 and 2 equiv of 5-ethynylthiophene-2-carboxylic acid (H-ThCCH) in toluene, the complexes trans-M2(T(i)PB)2(ThCCH)2, where M = Mo (I) or W (II) and T(i)PB = 2,4,6-triisopropyl benzoate, have been isolated and characterized by (1)H NMR, IR, MALDI-TOF MS, UV-vis, steady-state emission, transient absorption, and time-resolved infrared (TRIR) spectroscopies and single-crystal X-ray crystallography for I. The molecular structure of I confirms the trans-substitution pattern and the extended conjugation of the ethynylthienyl ligands via interaction with the Mo2δ orbital. The HOMO of both I and II is the M2δ orbital, and the intense color of the compounds (I is red and II is blue) is due to the M2δ-to-ThCCH (1)MLCT transition. The S1 states for I and II are (1)MLCT. The T1 state is (3)MLCT for II, but (3)MoMoδδ* for I. The TRIR spectra of the ν(C≡C) stretch in the MLCT states are consistent with the delocalization of the electron over both ThCCH ligands. Compound I is shown to be a synthon for the preparation of trans-Mo2(T(i)PB)2(ThCCPh)2 (III) and trans-Mo2(T(i)PB)2(ThCCAuPPh3)2 (IV). Both III and IV have been characterized spectroscopically and by single-crystal X-ray diffraction. The structure of III indicates the extended π-conjugation of the trans-ethynyl-thienyl units extends to the added phenyl rings.

Coordination of N,N-chelated Re(CO)3Cl units across a Mo2 quadruple bond: synthesis, characterization, and photophysical properties of a Re-Mo2-Re triad and its component pieces.

2-(2-Pyridyl)-4-methylthiazole carboxylic acid (PMT-H) and rhenium tricarbonyl chloride react to form the red crystalline compound fac-Re(PMT-H)(CO)3Cl, I, which is an analog of the well-known Re(bpy)(CO)3Cl molecule, where bpy is 2,2'-bipyridine. The acids PMT-H (2 equiv) and Re(PMT-H)(CO)3Cl (2 equiv) also react with Mo2(T(i)PB)4 (T(i)PB = 2,4,6-triisopropylbenzoate) in toluene to give the red compound trans-Mo2(T(i)PB)2(PMT)2, II, and the royal blue compound trans-Mo2(T(i)PB)2[(PMT)Re(CO)3Cl]2, III, respectively. The X-ray and spectroscopic characterization of I confirms its close relationship with Re(bpy)(CO)3Cl, as does the spectroscopic characterization of compounds II and III as analogs of other compounds of the form trans-M2(TiPB)2L2, where L is a π-acceptor ligand. Electronic structure calculations on model compounds II' and III', where formate ligands substitute for T(i)PB, show that the highest occupied molecular orbital (HOMO) in II is Mo2δ. When the Re(CO)3Cl unit is attached to the PMT ligand to form III, this orbital is stabilized significantly and now becomes associated with a close in energy band of Re d(6), t2g type orbitals. Oxidation of III is shown to be Mo2-based, as evident by EPR spectroscopy, and the lowest-energy electronic absorption corresponds to a Mo2δ-to-PMT π* transition. The S1 states in both II and III are metal-to-ligand charge-transfer (MLCT), and the lowest-energy triplet sate, T1 is (3)MoMoδδ*, as evidenced by its steady state emission spectral features. The excited states of compounds I (T1) and III (S1 and T1) have been investigated by time-resolved infrared spectroscopy (TRIR). The spectral features of I parallel those for Re(bpy)(CO)3Cl, with the lowest-energy T1 state corresponding to Re dπ to PMT-H π* charge transfer, producing higher-energy CO stretching vibrations relative to the ground state. For III, the CO vibrations are shifted to lower energy, consistent with charge being located on the PMT ligand, which enhances Re-to-CO backbonding. In the MoMoδδ* T1 state, however, the backbonding is reduced to the PMT ligand, and the CO stretches are at slightly higher energy relative to the ground state.

Concerning the ground state and S1 and T1 photoexcited states of the homoleptic quadruply bonded complexes Mo2(O2CC6H4-p-X)4, where X = C≡C-H or C≡N.

The preparation of the homoleptic MM quadruply bonded complexes Mo2(O2CC6H4-p-X)4, where X = C≡C-H (I) or C≡N (II), is reported along with the solution characterization data and electronic structure calculations employing density functional theory. The compounds are colored orange (I) and red (II) due to the metal-to-ligand charge transfer involving the HOMO, Mo2δ, and LUMO, which is a ligand-based π* combination. Studies of the S1 state, (1)MLCT, by femtosecond time-resolved infrared spectroscopy indicate that the negative charge is distributed principally over two trans ligands. The T1 states are (3)MoMoδδ* as determined by NIR emission and nanosecond transient absorption.

Electronic structure and excited-state dynamics of the molecular triads: trans-M2(T(i)PB)2[O2CC6H5-η6-Cr(CO)3]2, where M = Mo or W, and T(i)PB = 2,4,6-triisopropylbenzoate.

From the reactions between M(2)(T(i)PB)(4) and HO(2)CC(6)H(5)-η(6)-Cr(CO)(3) (2 equiv), the title compounds trans-M(2)(T(i)PB)(2)[O(2)CC(6)H(5)-η(6)-Cr(CO)(3)](2), where M = Mo or W, and T(i)PB = 2,4,6-triisopropylbenzoate have been prepared and characterized. Compound I (M = Mo) was characterized by a single crystal X-ray structural determination which revealed a centrosymmetric MoMo quadruply bonded molecule. Compound I is red and the tungsten complex II is blue as a result of intense metal-to-ligand charge transfer (MLCT), which is principally M(2)δ to benzoate π* with some chromium t(2g) participation, according to calculations employing density functional theory. Compound I shows dual emission from S(1) and T(1) states that are assigned (1)MLCT and (3) MoMoδδ*, respectively. Both complexes have been studied by time-resolved infrared spectroscopy (TRIR) in the region of the carbonyl stretching frequency. Compound II displays a shift of ν(CO) to lower energy in both the (1)MLCT and (3)MLCT states in THF, while I in CH(2)Cl(2) shows ν(CO) bands shifted to both higher and lower energy. We attribute the shift to higher energy seen for I to a Cr t(2g) to benzoate π* transition which mixes with the Mo(2)δ to benzoate charge transfer upon excitation at 514 nm. In THF compound I undergoes a reversible photodissociation, potentially due to CO loss. Based on the TRIR of the carbonyl vibrations, it is proposed that the MLCT states are delocalized over both benzoate Cr(CO)(3) groups, as supported by calculations.

MM Quadruply Bonded Complexes Supported by Vinylbenzoate Ligands: Synthesis, Characterization, Photophysical Properties and Application as Synthons.

From the reactions between M2(T i PB)4 compounds and meta and para - vinylbenzoic acids (2 equiv) in toluene at room temperature the compounds trans-M2(T i PB)2L2, where L = m-vinylbenzoate 1A (M = Mo) and 1B (M = W) and T i PB = 2,4,6-triisopropylbenzoate, and where L = p-vinylbenzoate 2A (M = Mo) and 2B (M = W) have been isolated. Compounds 1A and 2A have been shown to undergo Heck carbon-carbon coupling reactions with phenyliodide to produce trans-Mo2(T i PB)2(O2CC6H4-m-CH=CH-C6H5)2,3A and trans-Mo2(T i PB)2(O2CC6H4-p-CH=CH-C6H5)2, 4A. The molybdenum compounds 1A and 2A have been structurally characterized by single crystal X-ray crystallography. All the new compounds have been characterized by 1H NMR, IR, UV-Visible absorption and emission spectroscopy, high resolution MALDITOF MS, fs- and ns- transient absorption spectroscopy and fs- time-resolved IR spectroscopy. Electronic structure calculations employing density functional theory, DFT, and time-dependent DFT have been employed to aid in the interpretation of spectral data. All compounds show intense absorptions in the visible region corresponding to M2δ to Lπ* charge transfer transitions. The lifetimes of the 1MLCT state fall in the range of 1 - 10 ps and for the molybdenum complexes the T1 states are 3δδ* with lifetimes ~50 µs while for the tungsten complexes the T1 are 3 MLCT with lifetimes in the range of 3 - 10 ns.

Photoinduced charge transfer involving a MoMo quadruply bonded complex to a perylene diimide.

Evidence, based on femtosecond transient absorption and time resolved infrared spectroscopy, is presented for photoinduced charge transfer from the Mo2δ orbital of the quadruply bonded molecule trans-Mo2(T(i)PB)2(BTh)2, where T(i)PB = 2,4,6-triisopropyl benzoate and BTh = 2,2'-bithienylcarboxylate, to di-n-octyl perylene diimide and di-n-hexylheptyl perylene diimide in thin films and solutions of the mixtures. The films show a long-lived charge separated state while slow back electron transfer, τBET ~ 500 ps, occurs in solution.

Modulating the M2δ-to-ligand charge transfer transition by the use of diarylboron substituents.

From the reactions between the quadruply bonded complexes M2(T(i)PB)4, where M = Mo or W and T(i)PB = 2,4,6-triisopropylbenzoate, and the carboxylic acids HOOC-C6H4-4-B(mesityl)2, LH (2 equivalents) the complexes trans-M2(T(i)PB)2L2 have been prepared. The new compounds have been characterized by (1)H NMR, MALDI-TOF MS, UV-Vis-NIR and steady-state emission spectroscopy, time-resolved transient absorption spectroscopy and cyclic voltammetry. These results are compared with the related properties of the benzoates, M2(T(i)PB)2(O2CPh)2 (prepared similarly) and with DFT calculations on model compounds where formate substitutes for T(i)PB. The new compounds M2(T(i)PB)2L2 are intensely colored in toluene or THF solutions: red (M = Mo) and green (M = W) and the introduction of the p-B(mesityl)2 group notably shifts these metal to ligand charge transfer transitions to lower energy in comparison to the benzoate complexes M2(T(i)PB)2(O2C-C6H5)2. Upon the addition of fluoride ions these intense absorptions are shifted to much higher energy in a reversible manner for M = Mo.

Photophysical properties of MM quadruply bonded complexes (M = Mo, W) supported by carboxylate ligands: charge delocalization and dynamics in S1 and T1 states.

Quadruply bonded dinuclear metal complexes of molybdenum and tungsten have the MM configuration σ(2)π(4)δ(2) and a considerable degree of attention has been devoted to studies of the δ → δ(*) transition. For compounds of the type M(2)(O(2)CR)(4), the CO(2) π(*) orbitals introduce a M(2) δ to ligand π(*) transition, a (1)MLCT absorption which may be lower in energy than the δ → δ(*) and is more intense, thus obscuring the observation of the latter. When the R group is a conjugated organic system such as an aryl group, the (1)MLCT shifts to even lower energy and emission is seen from this S(1) state in addition to phosphorescence from the T(1) state which may be either (3)MLCT or (3)MMδδ(*). The latter typically occurs around 1100 nm with a lifetime that ranges from ~1 µs (M = W) to 100 µs (M = Mo). The S(1)(1)MLCT states have lifetimes of ~1-20 ps, allowing for fs and ns studies of the charge distribution/localization with time in both the S(1) and T(1) states, which is quite rare for transition metal coordination complexes. Of particular interest and focus have been complexes of the type trans-M(2)L(2)L'(2) where L and L' are carboxylate or amidinate groups for which only one set of ligands allows for expansive Lπ-M(2)δ-Lπ conjugation and has a low energy (1)MLCT. Compounds of this type have excited states that may be considered as mixed valence (MV) ions [L-M(2)(+)-L(-)] ↔ [L(-)-M(2)(+)-L] where the hole resides on the M(2) unit and the electron is either localized on one ligand, a class I or II MV ion, or is fully delocalized over both ligands, a class III ion in the Robin and Day scheme. Examples of these systems will be described along with the newly prepared complexes trans-M(2)(T(i)PB)(2)(O(2)CC≡C-9-anthracene)(2), M = Mo, W, that have the IR-active reporter groups CO(2) and C≡C.

Furan- and selenophene-2-carboxylato derivatives of dimolybdenum and ditungsten (M[quadruple bond]M): a comparison of their chemical and photophysical properties.

From the reactions between M(2)(T(i)PB)(4), where T(i)PB = 2,4,6-triisopropylbenzoate and two equivalents each of 2-furan carboxylic acid, FuCO(2)H, and 2-selenophene carboxylic acid, SpCO(2)H in toluene, the new compounds trans-M(2)(T(i)PB)(2)(O(2)CFu)(2) (1a M = Mo, 2a M = W) and trans-M(2)(T(i)PB)(2)(O(2)CSp)(2) (1b M = Mo, 2b M = W) were formed. These new compounds have been characterized by (1)H NMR, steady-state UV-Vis-NIR absorption and emission spectroscopy, cyclic and differential pulse voltammetry, and fs and ns transient absorption spectroscopy. The compound Mo(2)(T(i)PB)(2)(O(2)CSp)(2) (1b) has been characterized by single crystal X-ray crystallography. These data are compared with those previously reported for related 2-thiophene carboxylate derivatives: M(2)(T(i)PB)(2)(O(2)CTh)(2). The physico-chemical data correlate well with electronic structure calculations performed on model compounds. All compounds have detectible S(1) photoexcited states with lifetimes that vary from ∼5 ps to < 1 ps. The molybdenum compounds have T(1) states with microsecond lifetimes that are assigned as MMδδ* whereas the T(1) states for tungsten are (3)MLCT with lifetimes on the order of nanoseconds. In all cases, shorter lifetimes were seen in complexes containing heavier atoms.

Molecular and electronic structures and photophysical properties of quadruply bonded dimetal complexes (M = Mo or W) supported by trans-arylethynylcarboxylate ligands where aryl = p-tolyl or 9-anthrancenyl.

From the reactions between M(2)(T(i)PB)(4), where T(i)PB = 2,4,6-triisopropylbenzoate and M = Mo or W, in toluene and each of the respective carboxylic acids (2 equiv) the quadruply MM bonded compounds trans-M(2)(T(i)PB)(2)(O(2)C-C≡C-Ar)(2) have been prepared where Ar = p-tolyl and M = Mo, , and M = W, , and Ar = 9-anthracenyl, where M = Mo, 2a, and M = W, 2b. Single crystal X-ray crystallographic studies of 1a and 2b confirmed the trans substitution pattern about the Mo(2)(4+) unit and the centrosymmetric molecules have structural features that indicate extensive Lπ-Mo(2)δ-Lπ conjugation involving the arylethynylcarboxylates. The compounds are intensely colored as a result of the HOMO → LUMO, metal δ-to-ligand π* charge transfer (1)MLCT transition: 1a (orange), 1b (red), 2a (blue) and 2b(green). The compounds 1a, 2a, 1b and 2b have been characterized by UV-Vis-NIR absorption and emission spectroscopy, cyclic voltammetry, femtosecond (fs) and nanosecond (ns) transient absorption spectroscopy and by fs time-resolved infrared spectroscopy in the region of ν(C≡C), ν(CO(2)) and from 1400-1000 cm(-1). Aided by density functional theory, (DFT) and time dependent DFT, the electronic structures of the ground state and the S(1) and T(1) states are described. The molybdenum compounds have short lived (1)MLCT states, 1a ~ 5.0 ps and 2a ~ 10.5 ps, that undergo intersystem crossing to long lived (3)MoMoδδ* states: 1a ~ 101 µs and 2a ~ 83 µs. The tungsten complexes show interesting time-resolved infrared spectra in the ν(C≡C) region when compared with their ground state. Compound 1b shows ν(C≡C) at 1975 cm(-1) for the (1)MLCT state which decays with τ ~ 0.7 ps to ν(C≡C) at 2000 cm(-1) for the (3)MLCT state. For 2b the (1)MLCT is characterized by ν(C≡C) at 2150 cm(-1), τ ~ 19 ps, and a very broad absorption with a maximum ~1970 cm(-1) which is proposed to arise from a low energy electronic transition. The (3)MLCT state for shows no evidence of ν(C≡C) and is suggested to have an electron localized principally on the anthracenyl portion of the ligand, a proposal that finds support from the nature of triplet transient absorption spectrum of 2b.