Platinum(ii) and palladium(ii) complexes with electron-deficient meso-diethoxyphosphorylporphyrins: synthesis, structure and tuning of photophysical properties by varying peripheral substituents.

A series of electron-deficient platinum(ii) and palladium(ii) meso-(diethoxyphosphoryl)porphyrins, namely [10-(diethoxyphosphoryl)-5,15-bis(p-tolyl)porphyrinato]palladium(ii) (PdDTolPP), {10-(diethoxyphosphoryl)-5,15-bis[p-(methoxycarbonyl)phenyl]porphyrinato}palladium(ii) [PdD(CMP)PP], [10-(diethoxyphosphoryl)-5,15-dimesitylporphyrinato]palladium(ii) (PdDMesPP), [5-(diethoxyphosphoryl)-10,15,20-trimesitylporphyrinato]palladium(ii) (PdTMesPP) and the corresponding platinum(ii) compounds, were synthesized and structurally characterized in solution by means of 1H, 13C, 31P NMR spectroscopies and in the solid state by single crystal X-ray diffraction [PdDTolPP, PdD(CMP)PP and PtD(CMP)PP]. Their optical and photophysical properties (UV-vis absorption, luminescence and excitation spectra, phosphorescence quantum yields and lifetimes) were also determined. The complexes under investigation emit at room temperature in the near-infrared region (670-770 nm). Phosphorescence quantum yields of the palladium(ii) meso-phosphorylated porphyrins lie in the range of 3.4 to 5.8%, with lifetimes of 633 to 858 µs in deoxygenated toluene solutions at room temperature. The corresponding platinum(ii) complexes exhibit phosphorescence quantum yields in the range of 9.2 to 11%, with luminescence decay times of 56 to 69 µs. Moreover, effective homogeneous oxygen quenching and good sensitivity in toluene (∼155 Pa-1 s-1) were observed for the platinum(ii) complexes with phosphorylporphyrins in solution. Investigations of the photostability of porphyrinylposphonates and related complexes lacking a phosphoryl group in DMF under irradiation in air using a 400 W vis-NIR lamp demonstrated that photobleaching is strongly dependent on the substituents at the periphery of the macrocycle. Platinum and palladium trimesitylphosphorylporphyrins PdTMesPP and PtTMesPP exhibit high photostability in DMF solution and seem to be the most potentially interesting derivatives of the series for oxygen sensing in biological samples and the covalent immobilization on solid supports to prepare sensing devices including optic fibers.

Coordination self-assembly through weak interactions in meso-dialkoxyphosphoryl-substituted zinc porphyrinates.

The self-assembly of seven zinc 10-(dialkoxyphosphoryl)-5,15-diarylporphyrinates Zn5-Zn11 containing different substituents at the phosphonate and aryl groups was investigated. Single crystals of Zn5-Zn9 complexes were grown under the same conditions and analyzed by X-ray structural analysis. A supramolecular self-assembly is observed in all crystals through weak coordinative bonding of the phosphoryl group of one porphyrin molecule to the zinc(ii) ion of a second molecule. The geometry of the porphyrin macrocycle is similar in all of the studied crystals and the central zinc atom in each case adopts a distorted tetragonal pyramidal environment. However, the Zn5-Zn7 porphyrins display a 1D polymeric structure while the Zn8 and Zn9 complexes exist as discrete cyclotetramers in the crystals. This data demonstrates that the non-coordinating meso-aryl substituents of meso-(dialkoxyphosphoryl)porphyrins influence their crystalline organization. A self-assembly of the Zn5-Zn11 complexes is also observed in toluene and chloroform solutions over a large temperature range (223-323 K). According to NMR studies, the associates exhibit dynamic behavior. A well-defined supramolecular aggregate of complex Zn10 at 10-3 M in toluene and chloroform solutions was unambiguously characterized as a cyclotetramer [Zn10]4 by 1H NMR spectroscopy at 223 K. The structure of the Zn10 association in toluene and chloroform shows a concentration dependence. When a solution of Zn10 in toluene was diluted from 10-3 M to 10-5 M, the average number of molecules in the associated unit decreased to about two.

Electrochemical, Spectroelectrochemical, and Structural Studies of Mono- and Diphosphorylated Zinc Porphyrins and Their Self-Assemblies.

Three series of porphyrins containing a Zn(II) central metal ion and zero, one, or two phosphoryl groups at the meso-positions of the macrocycle were characterized as to their electrochemical, spectroscopic, and structural properties in nonaqueous media. The investigated compounds are represented as 5,15-bis(4'-R-phenyl)porphyrinatozinc, 10-(diethoxyphosphoryl)-5,15-bis(4'-R-phenyl)porphyrinatozinc, and 5,15-bis(diethoxyphosphoryl)-10,20-bis(4'-R-phenyl)porphyrinatozinc, where R = OMe, Me, H, or CN. Linear-free energy relationships are observed between the measured redox potentials at room temperature and the electronic nature of the substituents at the 5 and 15 meso-phenyl groups of the macrocycle. The mono- and bis-phosphoryl derivatives with two p-cyanophenyl substituents provide electrochemical evidence for aggregation at low temperature, a greater degree of aggregation being observed in the case of 5,15-bis(diethoxyphosphoryl)-10,20-bis(4'-cyanophenyl)porphyrinatozinc(II). This compound was characterized in further detail by variable-temperature 1H and 31P{1H} NMR spectroscopy in solution combined with single crystal X-ray analysis in the solid state. The data obtained from these measurements indicate that this porphyrin has a dimeric structure in CDCl3 at 223-323 K but forms a 2D polymeric network when it is crystallized from a CHCl3/MeOH mixture.

Gallium(III) and Indium(III) Complexes with meso-Monophosphorylated Porphyrins: Synthesis and Structure. A First Example of Dimers Formed by the Self-Assembly of meso-Porphyrinylphosphonic Acid Monoester.

The synthesis and structural characterization, both in solution by means of 1H and 31P NMR and UV-vis spectroscopies and in the solid state by X-ray diffraction on single crystal, of a series of gallium(III) and indium(III) meso-mono(diethoxyphosphoryl)porphyrins bearing different peripheral substituents as well as the corresponding monoesters and phosphonic acids are reported. This work describes the first example of the X-ray structure of a self-assembled dimer formed via strong binding between the oxygen atom of the phosphonate substituent and the gallium(III) cations of adjacent porphyrin molecules [Ga-O = 1.9708(13) Å].

Conformational and structural studies of N-methylacetohydroxamic acid and of its mono- and bis-chelated uranium(VI) complexes.

The thermodynamics and kinetics of the cis/trans isomerism of N-methylacetohydroxamic acid (NMAH) and its conjugated base (NMA(-)) have been reinvestigated in aqueous media by (1)H NMR spectroscopy. Hindered rotation around the central C-N bond due to electronic delocalization becomes slow enough on the NMR time scale to observe both rotamers in equilibrium in D2O at room temperature. By properly assigning the methyl group resonances, evidence for the prevalence of the E over the Z form is unambiguously provided [K300=[E]/[Z]=2.86(2) and 9.63(5) for NMAH and NMA(-), respectively], closing thereby a long-lasting dispute about the most stable conformer. To that end, calculations of the chemical shifts by density functional theory (DFT), which accurately reproduced the experimental data, turned out to be a much more reliable method than the direct computation of the relative energy for each conformer. The Z ⇌ E interconversion dynamics was probed at 300 K in D2O by 2D exchange-correlated spectroscopy (EXSY), affording the associated rate constants [kZE=9.0(2) s(-1) and kEZ=3.14(5) s(-1) for NMAH, kZE=0.96(3) s(-1) and kEZ=0.10(2) s(-1) for NMA(-)] and activation barriers at 300 K [ΔG(≠)ZE=68.0 kJ mol(-1) and ΔG(≠)EZ=70.6 kJ mol(-1) for NMAH, ΔG(≠)ZE=73.6 kJ mol(-1) and ΔG(≠)EZ=79.2 kJ mol(-1) for NMA(-)]. For the first time, mono- and bis-chelated uranium(VI) complexes of NMA(-) have been isolated. Crystals of [UO2(NMA)(NO3)(H2O)2] and [UO2(NMA)2(H2O)] have been characterized by X-ray diffractometry, infrared and Raman spectroscopies.

Electrochemical and spectroelectrochemical studies of diphosphorylated metalloporphyrins. Generation of a phlorin anion product.

Two series of diphosphoryl-substituted porphyrins were synthesized and characterized by electrochemistry and spectroelectrochemistry in nonaqueous media containing 0.1 M tetra-n-butylammonium perchlorate (TBAP). The investigated compounds are 5,15-bis(diethoxyphosphoryl)-10,20-diphenylporphyrins (Ph)2(P(O)(OEt)2)2PorM and 5,15-bis(diethoxyphosphoryl)-10,20-di(para-carbomethoxyphenyl)porphyrins (PhCOOMe)2(P(O)(OEt)2)2PorM where M = 2H, Co(II), Ni(II), Cu(II), Zn(II), Cd(II), or Pd(II). The free-base and five metalated porphyrins with nonredox active centers undergo two ring-centered oxidations and two ring-centered reductions, the latter of which is followed by a chemical reaction of the porphyrin dianion to give an anionic phlorin product. The phlorin anion is electroactive and can be reoxidized by two electrons to give back the starting porphyrin, or it can be reversibly reduced by one electron at more negative potentials to give a phlorin dianion. The chemical conversion of the porphyrin dianion to a phlorin anion proceeds at a rate that varies with the nature of the central metal ion and the solvent. This rate is slowest in the basic solvent pyridine as compared to CH2Cl2 and PhCN, giving further evidence for the involvement of protons in the chemical reaction leading to phlorin formation. Calculations of the electronic structure were performed on the Ni(II) porphyrin dianion, and the most favorable atoms for electrophilic attack were determined to be the two phosphorylated carbon atoms. Phlorin formation was not observed after the two-electron reduction of the cobalt porphyrins due to the different oxidation state assignment of the doubly reduced species, a Co(I) π anion radical in one case and an M(II) dianion for all of the other derivatives. Each redox reaction was monitored by thin-layer UV-visible spectroelectrochemistry, and an overall mechanism for each electron transfer is proposed on the basis of these data.

The skeleton of the staghorn coral Acropora millepora: molecular and structural characterization.

The scleractinian coral Acropora millepora is one of the most studied species from the Great Barrier Reef. This species has been used to understand evolutionary, immune and developmental processes in cnidarians. It has also been subject of several ecological studies in order to elucidate reef responses to environmental changes such as temperature rise and ocean acidification (OA). In these contexts, several nucleic acid resources were made available. When combined to a recent proteomic analysis of the coral skeletal organic matrix (SOM), they enabled the identification of several skeletal matrix proteins, making A. millepora into an emerging model for biomineralization studies. Here we describe the skeletal microstructure of A. millepora skeleton, together with a functional and biochemical characterization of its occluded SOM that focuses on the protein and saccharidic moieties. The skeletal matrix proteins show a large range of isoelectric points, compositional patterns and signatures. Besides secreted proteins, there are a significant number of proteins with membrane attachment sites such as transmembrane domains and GPI anchors as well as proteins with integrin binding sites. These features show that the skeletal proteins must have strong adhesion properties in order to function in the calcifying space. Moreover this data suggest a molecular connection between the calcifying epithelium and the skeletal tissue during biocalcification. In terms of sugar moieties, the enrichment of the SOM in arabinose is striking, and the monosaccharide composition exhibits the same signature as that of mucus of acroporid corals. Finally, we observe that the interaction of the acetic acid soluble SOM on the morphology of in vitro grown CaCO3 crystals is very pronounced when compared with the calcifying matrices of some mollusks. In light of these results, we wish to commend Acropora millepora as a model for biocalcification studies in scleractinians, from molecular and structural viewpoints.

Unusual formation of a stable 2D copper porphyrin network.

Copper(II) 5,15-bis(diethoxyphosphoryl)-10,20-diphenylporphyrin was obtained and characterized by means of cyclic voltammetry, electron paramagnetic resonance, Fourier transform infrared, and UV-visible spectroscopy. Three crystalline forms were grown and studied by means of X-ray diffraction methods (single crystal and powder). The highly electron-withdrawing effect of phosphoryl groups attached directly to the porphyrin macrocycle results in a self-assembling process, with formation of a stable 2D coordination network, which is unusual for copper(II) porphyrins. The resulting 2D structure is a rare example of an assembly based on copper(II) porphyrins where the copper(II) central metal ion is six-coordinated because of a weak interaction with two phosphoryl groups of adjacent porphyrins. The other polymorph of copper(II) 5,15-bis(diethoxyphosphoryl)-10,20-diphenylporphyrin contains individual (isolated) porphyrin molecules with four-coordinated copper(II) in a distorted porphyrin core. This polymorph can be obtained only by slow diffusion of a copper acetate/methanol solution into solutions of free base 5,15-bis(diethoxyphosphoryl)-10,20-diphenylporphyrin in chloroform. It converts to the 2D structure after dissolution in chloroform followed by consecutive crystallizations, using slow diffusion of hexane. A six-coordinated copper(II) porphyrin containing two axially coordinated dioxane molecules was also obtained and characterized by X-ray diffraction crystallography. The association of copper(II) 5,15-bis(diethoxyphosphoryl)-10,20-diphenylporphyrin in solution was also studied.

Synthesis and self-organization of zinc ß-(dialkoxyphosphoryl)porphyrins in the solid state and in solution.

The first synthesis and self-organization of zinc ß-phosphorylporphyrins in the solid state and in solution are reported. ß-Dialkoxyphosphoryl-5,10,15,20-tetraphenylporphyrins and their Zn(II) complexes have been synthesized in good yields by using Pd- and Cu-mediated carbon-phosphorous bond-forming reactions. The Cu-mediated reaction allowed to prepare the mono-ß-(dialkoxyphosphoryl)porphyrins 1 Zn-3 Zn starting from the ß-bromo-substituted zinc porphyrinate ZnTPPBr (TPP = tetraphenylporphyrin) and dialkyl phosphites HP(O)(OR)(2) (R = Et, iPr, nBu). The derivatives 1 Zn-3 Zn were obtained in good yields by using one to three equivalents of CuI. When the reaction was carried out in the presence of catalytic amounts of palladium complexes in toluene, the desired zinc derivative 1 Zn was obtained in up to 72% yield. The use of a Pd-catalyzed C-P bond-forming reaction was further extended to the synthesis of ß-poly(dialkoxyphosphoryl)porphyrins. An unprecedented one-pot sequence involving consecutive reduction and phosphorylation of H(2)TPPBr(4) led to the formation of a mixture of the 2,12- and 2,13-bis(dialkoxy)phosphorylporphyrins 5 H(2) and 6 H(2) in 81% total yield. According to the X-ray diffraction studies, 1 Zn and 3 Zn are partially overlapped cofacial dimers formed through the coordination of two Zn centers by two phosphoryl groups belonging to the adjacent molecules. The equilibrium between the monomeric and the dimeric species exists in solutions of 1 Zn and 3 Zn in weakly polar solvents according to spectroscopic data (UV/Vis absorption and NMR spectroscopy). The ratio of each form is dependent on the concentration, temperature, and traces of water or methanol. These features demonstrated that zinc ß-phosphorylporphyrins can be regarded as new model compounds for the weakly coupled chlorophyll pair in the photosynthesis process.

Acceleration of the through space S1 energy transfer rates in cofacial bisporphyrin bio-inspired models by virtue of substituents effect on the Förster J integral and its implication in the antenna effect in the photosystems.

The singlet k(ET) for cofacial ß-octaalkylporphyrin/bis(meso-aryl)porphyrin dyads increases linearly with the gap between the donor-acceptor 0-0 fluorescence peaks at 77 K.

Singlet and triplet energy transfer rate acceleration by additions of clusters in supramolecular pigment-organometallic cluster assemblies.

Both S(1) and T(1) energy transfer rates (porphyrin → cluster) increase from mono- to di- to tetracarboxylate[tetraphenyl-(zinc)porphyrin] adducts with [Pd(3)(dppm)(3)(CO)](2+) clusters.

Synthesis of meso-polyphosphorylporphyrins and example of self-assembling.

Pd-catalyzed coupling reactions have been used to prepare meso-phosphorylporphyrins. A 2D metal-organic network formed via P horizontal lineO...Zn axial supramolecular coordination of 5,15-bis(diethoxyphosphoryl)-10,20-diphenylporphyrin is the first example of a 2D framework based on phosphorylporphyrin derivatives.

Triplet energy transfers in electrostatic host-guest assemblies of unsaturated organometallic cluster cations and carboxylate-containing porphyrin pigments.

The unsaturated cyclic [M3(dppm)3(CO)](2+) clusters (M = Pt, Pd; dppm = Ph2PCH2PPh2; such as PF6(-) salt) exhibit a cavity formed by the six dppm-phenyl groups placed like a picket fence above the unsaturated triangular M3 dicationic center. Electrostatic interactions of the M(3+) units inside this cavity with the carboxylate anion RCO2(-) [R = tetraphenylporphyrinatozinc(II), ZnTPP; p-phenyltritolylporphyrinatozinc(II), ZnTTPP; p-phenyltritolylporphyrinatopalladium(II), PdTTPP] form dyads for through-space triplet energy transfers. The binding constants are on the order of 20,000 M(-1) in all six cases (298 K). The energy diagram built upon absorption and emission spectra at 298 and 77 K places the [Pt3(dppm)3(CO)](2+) and [Pd3(dppm)3(CO)](2+) as triplet energy donors, respectively, with respect to the ZnTPPCO2(-), ZnTTPPCO2(-), and PdTTPPCO2(-) pigments, which act as acceptors. Evidence for energy transfer is provided by the transient absorption spectra at 298 K, where triplet-triplet absorption bands of the metalloporphyrin chromophores are depicted at all time (at 298 K) with total absence of the charge-separated state in the nanosecond to microsecond time scale. Rates for energy transfer (ranging in the 10(4) s(-1) time scale) are extracted from the emission lifetimes of the [Pt3(dppm)3(CO)](2+) donor in the free chromophore and the host-guest assemblies. The emission intensity of [Pd3(dppm)3(CO)](2+) is too weak to measure its spectrum and emission lifetime in the presence of the strongly luminescent metalloporphyrin-containing materials. For the [Pd3(dppm)3(CO)](2+)...metalloporphyrin dyads, evidence for fluorescence and phosphorescence lifetime quenching of the porphyrin chromophore at 298 K is provided. These quenchings, exhibiting rates of 10(4) (triplet) and 10(8) s(-1) (singlet), are attributed to a photoinduced electron transfer from the metalloporphyrin to the cluster due to the low reduction potential.

Comments on the through-space singlet energy transfers and energy migration (exciton) in the light harvesting systems.

Recent findings on the photophysical investigations of several cofacial bisporphyrin dyads for through space singlet and triplet energy transfers raised several serious questions about the mechanism of the energy transfers and energy migration in the light harvesting devices, notably LH II, in the heavily studied purple photosynthetic bacteria. The key issue is that for simple cofacial or slipped dyads with controlled geometry using rigid spacers or spacers with limited flexibilities, the fastest possible rates for singlet energy transfer for three examples are in the 10 x 10(9)s(-1) (i.e. just in the 100 ps time scale) for donor-acceptor distances approaching 3.5-3.6 A. The reported time scale for energy transfers between different bacteriochlorophylls, notably B800*-->B850, is in the picosecond time scale despite the long Mg...Mg separation of approximately 18 A. Such a short rate drastically contrasts with the well accepted Förster theory. This article reviews the modern knowledge of the structure, bacteriochlorophyll a transition moments, and photophysical processes and dynamics in LH II, and compares these parameters with the recently investigated model bisporphyrin dyads build upon octa-etio-porphyrin chromophores and rigid and semi-rigid spacers. The recently discovered role of the rhodopin glucoside residue called carotenoid will be commented as the possible relay for energy transfer, including the possibility of uphill processes at room temperature. In this context, the concept of energy migration, called exciton, may also be affected by relays and uphill processes. Also, it is becoming more and more apparent that the presence of an irreversible electron transfer reaction at the reaction center, i.e. electron transfer from the special pair to the phyophytin macrocycle and so on, renders the rates for energy transfer and migration more rapid precluding all possibility of back transfers.

Self-organization of porphyrin units induced by magnetic field during sol-gel polymerization.

The use of a magnetic field as a controlling factor during the hydrolysis-polycondensation of porphyrin precursors substituted by Si(OR)(3) groups, induces a self-organization of porphyrin moieties due to the stacking of these units in the hybrid material and this study also confirms the effect of the magnetic field in the nano- and micrometric organization during the kinetically controlled polycondensation process.

Photophysical properties of a rhodium tetraphenylporphyrin-tin corrole dyad. The first example of a through metal-metal bond energy transfer.

The luminescence spectroscopy study and the determination of the photophysical parameters for the M-M'-bonded rhodium meso-tetraphenylporphyrin-tin(2,3,7,13,17,18-hexamethyl-8,12-diethylcorrole) complex, (TPP)Rh-Sn(Me6Et2Cor) 1, was investigated. The emission bands as well as the lifetimes (tau(e)) and the quantum yields (Phi(e); at 77 K using 2MeTHF as solvent) were compared with those of (TPP)RhI 2 (TPP = tetraphenylporphyrin) and (Me6Et2Cor)SnCl 3 (Me6Et2Cor = 2,3,7,13,17,18-hexamethyl-8,12-diethylcorrole) which are the two chemical precursors of 1. The energy diagram has been established from the absorption, fluorescence and phosphorescence spectra. The Rh(TPP) and Sn(Me6Et2Cor) chromophores are the energy donor (D) and acceptor (A), respectively. The total absence of fluorescence in 1 (while fluorescence is observed in the tin derivative 3) indicates efficient excited state deactivation, presumably due to heavy atom effect and intramolecular energy transfer (ET). The large decreases in tau(P) and Phi(P) of the Rh(TPP) chromophore going from 2 to 1 indicate a significant intramolecular ET in the triplet states of 1 with an estimated rate ranging between 10(6) and 10(8) s(-1). Based on the comparison of transfer rates with other related dyads that exhibit similar D-A separations and no M-M' bond, and for which slower through space ET processes (10(2)-10(3) s(-1)) operate, a through M-M' bond ET has been unambiguously assigned to 1.

Synthesis and photophysical properties of meso-substituted bisporphyrins: comparative study of phosphorescence quenching for dioxygen sensing.

The 4,6-bis(10-mesityl-5,15-di-p-tolylporpyrinyl)dibenzothiophene (H4DPSN) free base was obtained in five steps from commercially available materials. The metalation of DPSN2- with zinc(II), copper(II), and palladium(II) led to three new homobimetallic systems, (Zn)2DPSN, (Cu)2DPSN, and (Pd)2DPSN, respectively. The cofacial structures of these molecules offer the possibility of having dioxygen molecules inside the cavity for a period of time, allowing dynamic (collisional) phosphorescence quenching to be more efficient. The bimolecular excited-state deactivation rate constant for deactivation by dioxygen (kQ: (Pd)2DPB, 2.98x10(9); (Pd)2DPSN, 3.99x10(9); (Pd)2DPX, 6.94x10(9); (Pd)TPP, 8.95x10(9); (Pd)2DPS, 8.95x10(9) M-1 s-1) of (Pd)2DPSN, which exhibits an intense phosphorescence at 699 nm, was compared to those observed for (Pd)TPP, (Pd)2DPS, (Pd)2DPX, and (Pd)2DPB (TPP2-=tetraphenylporphyrin dianion, DPS4-=4,6-bis[5-(2,8,13,17-tetraethyl-3,7,12,18-tetramethylporphyrinyl)]dibenzothiophene tetraanion, DPX4-=4,5-bis[5-(2,8,13,17-tetraethyl-3,7,12,18-tetramethylporphyrinyl)]-9,9-dimethylxanthene tetraanion, and DPB4-=1,8-bis[5-(2,8,13,17-tetraethyl-3,7,12,18-tetramethylporphyrinyl)]biphenylene tetraanion). These collision-induced deactivation data were interpreted by estimating a series of physical parameters such as the surface area and bisporphyrin radii, the diffusion coefficient of the bismacrocycles, and the theoretical deactivation efficiency for the five compounds addressing the role of steric hindrance of the macrocycles on each other and the aryl groups at the meso positions. For sensing purposes, (Pd)2DPX is characterized by a Stern-Volmer constant kSV of 2.91x10(6) M-1, placing the lower detection limit for [O2] in solution at 0.58 ppm, which is better than that for (Pd)TPP (kSV=2.31x10(6) M-1; lower detection limit of 0.73 ppm), the classically used monoporphyrin complex.

Triplet-triplet energy transfer controlled by the donor-acceptor distance in rigidly held palladium-containing cofacial bisporphyrins.

Eleven new complexes, including mono-, heterobi-, and homobimetallic cofacial bisporphyrins, (Pd)H2DPS, (M)H2DPX, (M)H2DPB, (PdZn)DPS, (PdZn)DPX, (Pt)2DPX, (M)2DPB (M = Pd, Pt), and (Pt)P (DPS4- = 4,6-bis[5-(2,8,13,17-tetraethyl-3,7,12,18-tetramethylporphyrinyl)]dibenzothiophene tetraanion, DPX(4-) = 4,5-bis[5-(2,8,13,17-tetraethyl-3,7,12,18-tetramethylporphyrinyl)]-9,9-dimethylxanthene tetraanion, DPB4- = 1,8-bis[5-(2,8,13,17-tetraethyl-3,7,12,18-tetramethylporphyrinyl)]biphenylene tetraanion, P2- = 5-phenyl-2,8,13,17-tetraethyl-3,7,12,18-tetramethylporphyrin dianion) have been synthesized and characterized. The photophysical properties of the donor (M)P (M=Pd or Pt, P=porphyrin chromophore) and the acceptor (free base H(2)P or (Zn)P) depend on the C(meso)-C(meso) distance and the presence of a heavy atom such as Pd(II) or Pt(II). The data were compared with those for the known compounds (Pd)2DPS, (Pd)2DPX, H4DPS, H4DPX, H4DPB, (Pd)P, (Zn)P, and H(2)P. The rate constants for triplet-triplet energy transfer (k(ET)) were measured for the heterobimetallic (PdZn) and monometallic [(M)H2] derivatives (M=Pd, Pt). The fluorescence lifetimes (Deltatau(F)) of the acceptors decrease as a result of the heavy-atom effect, and vary as follows: (Pd)H2DPS<<(Pd)H2DPX approximately (Pd)H2DPB. The k(ET) values calculated according to the equation k(ET)=(1/tau(emi)-1/tau(emi) (0)), where tau(emi) (0) is the emission lifetime of the homobimetallic bisporphyrins (no ET occurs), are equal to 0, 247+/-57 and 133+/-52 s(-1) for DPS, DPX, and DPB, respectively, in the (Pd)H(2) series. These measurements allowed the range of distance over which the Dexter mechanism for T(1)-T(1) energy transfer ceases to operate to be determined. This distance is somewhere between 4.3 and 6.3 A, in agreement with our recent findings on singlet-singlet energy transfer. During the course of this study, the X-ray crystal structure for (Pd)H2DPX was obtained; triclinic (P1), a = 11.1016(1), b = 14.9868(2), c = 20.6786(3) A, alpha = 102.091(1), beta = 100.587(1), gamma = 101.817(1) degrees , V = 3199.19(7) A(3), Z = 2.

Synthesis, characterization, and photophysical properties of a free base and a biszinc(II) complex of 1,3-bisporphyrincalix[4]arene: evidence for "tunable intramolecular open and closed conformations".

The bismacrocycle 5,17-bis[5-(2,8,13,17-tetraethyl-3,7,12,18-tetramethylporphyrinyl)]-25,26,27,28-tetrapropoxycalix[4]arene (4) was synthesized in three steps from the corresponding bisaldehyde 5,17-diformyl-25,26,27,28-tetrapropoxycalix[4]arene. The biszinc(II) complex (5) was prepared as well, and the photophysical properties were measured using 2-MeTHF as solvent at 298 and 77 K. While computer modeling for 5 predicts that both pinched cone conformers, closed (porphyrins near each other) and open (porphyrins away from each other), may exist in the "gas phase", the experimental data indicate clearly that no zinc porphyrin...zinc porphyrin interactions are present in solution at 298 K, favoring the open conformer, where the two macrocycles are placed away from each other. On the other hand, clear evidence for a closed conformer is observed at 77 K. Variable-temperature (1)H NMR experiments show that 5 is fluxional between 298 and 183 K, while 4 keeps the open conformation for the whole temperature range. This behavior is unprecedented for calix[4]areneporphyrin compounds, and the relative porphyrin ring rigidity is postulated to explain this difference.