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Stable Singlet Biradicals of Rare-Earth-Fused Diporphyrin-Triple-Decker Complexes Having Low Energy Gaps and Multi-Redox States
摘要： Dinuclear rare-earth (TbIII, YIII) triple-decker complexes with a fused-diporphyrin (FP) and two tetraphenylporphyrin (TPP) ligands were synthesized in neutral, dianionic, and diprotonated forms. The neutral forms have large open shell biradical character, as determined from the temperature dependency of the magnetic susceptibility measurements and theoretical calculations. The coupling value (J = ?1.4 kcal mol?1, ?487 cm?1) of the radical centers in the neutral form of the YIII complex indicates weak pairing interactions. Theoretical calculations on the neutral form reveal a significant biradical character (y = 68%). Furthermore, the TbIII complex exhibits multi-redox states, having more than eight clear peaks in the voltammetry curves. The optical (3700 nm, 0.33 eV) and electrochemical measurements (3400 nm, 0.36 eV) indicate that the neutral form has very small HOMO?LUMO energy gap. Despite the large biradical character, the neutral complexes are thermally stable and do not decompose on heating at 120 ?C. These complexes with unique characteristics are promising candidates for use in molecular electronics, optics, and spintronics.
关键词： rare earths,redox chemistry,radicals,sandwich complexes,porphyrinoids
更新于2025-09-23 15:22:29
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Planar Antiaromatic Core-Modified 24π Hexaphyrin(1.0.1.0.1.0) and 32π Octaphyrin(1.0.1.0.1.0.1.0) Bearing Alternate Hybrid-Diheterole Units
摘要： Lewis acid catalyzed self-condensation of hybrid diheterole (furan-pyrrole and thiophene-pyrrole) precursors afforded novel Hückel antiaromatic 24π hexaphyrin(1.0.1.0.1.0) and 32π octaphyrin(1.0.1.0.1.0.1.0) without β-annulated bridges. Single-crystal X-ray diffraction analysis of the hybrid porphyrinoids (S3N3-ox and O4N4-ox) revealed nearly planar conformation and the 1H NMR spectra suggested the presence of paratropic ring currents. These antiaromatic macrocycles showed the characteristic optical features and undergo reversible two-electron reduction to Hückel aromatic 26π- and 34π-electron species, respectively, as is evident from the spectroscopic and theoretical studies (NICS and ACID calculations). Implementation of hybrid diheteroles alternately into the expanded porphyrin skeletons would be a novel approach for fine-tuning of the electronic structures of the planar antiaromatic macrocycles.
关键词： cyclization,antiaromaticity,conformation,redox,porphyrinoids
更新于2025-09-23 15:22:29
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Excitonically Coupled Cyclic BF2 Arrays of Calix[8]a?? and Calix[16]phyrin as Neara??IRa?? Chromophores
摘要： A pair of giant calix[n]phyrin derivatives namely calix[8]- (4) and calix[16]phyrin (5), involving two and four BF2 units, respectively, were prepared via the condensation of bis-naphthobipyrrolylmethene-BF2 complex with pentafluorobenzaldehyde. Both systems and precursor 3 were fully characterized, including via single crystal X-ray diffraction analyses. Calix[n]phyrins 4 and 5 display extremely high extinction coefficients (3.67 and 4.82 105 M-1cm-1, respectively) in the near-IR region. This observation was taken as initial evidence for strong excitonic coupling within these cyclic multi-chromophoric systems. Detailed insights into the effect of excitonic coupling dynamics on the electronic structure and photophysical properties of the macrocycles came from fluorescence, time-correlated single-photon counting (TCSPC) and transient absorption (TA) measurements. Support for the experimental findings came from theoretical studies. Taken in concert this combination of theory and experiment served to confirm that the coupling between the excitons depends on the specifics of the calix[n]phyrin structure, not just its size.
关键词： Cyclic BODIPY,Boron,Exciton Coupling,Porphyrinoids,NIR Dye,Calix[n]phyrin
更新于2025-09-23 15:19:57
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Excitonically Coupled Cyclic BF2 Arrays of Calix[8]a?? and Calix[16]phyrin as Neara??IRa?? Chromophores
摘要： A pair of giant calix[n]phyrin derivatives namely calix[8]- (4) and calix[16]phyrin (5), involving two and four BF2 units, respectively, were prepared via the condensation of the bis-naphthobipyrrolylmethene-BF2 complex with pentafluorobenzaldehyde. Both systems and precursor 3 were fully characterized, including via single crystal X-ray diffraction analyses. Calix[n]phyrins 4 and 5 display extremely high extinction coefficients (3.67 and 4.82 105 M-1cm-1, respectively) in the near-IR region. This observation was taken as initial evidence for strong excitonic coupling within these cyclic multi-chromophoric systems. Detailed insights into the effect of excitonic coupling dynamics on the electronic structure and photophysical properties of the macrocycles came from theoretical studies. Taken in concert this combination of theory and experiment served to confirm that the coupling between the excitons depends on the specifics of the calix[n]phyrin structure, not just its size.
关键词： Cyclic BODIPY,Boron,Exciton Coupling,Porphyrinoids,NIR Dye,Calix[n]phyrin
更新于2025-09-23 15:19:57
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Synergy of light harvesting and energy transfer as well as short-range charge shift reactions in multicomponent conjugates
摘要： We report herein on the design, the synthesis, and the characterization of a panchromatic, charge stabilizing electron donor–acceptor conjugate: (BBPA)3–ZnPor–ZnPc–SubPc 1. Each component, that is, bis(biphenyl)phenylamine (BBPA), Zn(II) porphyrin (ZnPor), Zn(II) phthalocyanine ZnPc, and subphthalocyanine (SubPc), has been carefully chosen and modified to enable a cascade of energy and charge transfer processes. On one hand, ZnPor, has been functionalized with three electron-donating BBPA as primary and secondary electron donors and to stabilize the final charge-separated state, and, on the other hand, a perfluorinated SubPc has been selected as ultimate electron acceptor. In addition, the ZnPc unit contains several trifluoromethylphenyl moieties to match its energy levels to those of the other components. In fact, irradiation of the heteroarray 1 triggers a cascade of light harvesting across the entire visible range, unidirectional energy transfer, exergonic charge separating, and short-range charge shifting to afford a (BBPA)3(cid:129)+–ZnPor–ZnPc–SubPc(cid:129)? charge-separated state. The lifetime of the latter reaches well into the range of tens of nanoseconds with a 14% quantum yield.
关键词： charge stabilizing,light harvesting,panchromatic,charge transfer,energy transfer,porphyrinoids,electron donor–acceptor conjugate
更新于2025-09-19 17:15:36
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Electrochemistry of zinc tetraarylporphyrins containing fused butano and benzo groups. Effect of solvent and substituents on spectra, potentials and mechanism in nonaqueous media
摘要： Two series of zinc tetraarylporphyrins containing four b,b′-pyrrole fused butano or benzo groups were synthesized and characterized as to their electrochemical and spectroelectrochemical properties in nonaqueous media. The examined compounds are represented as butano(Ar)4PorZn and benzo(Ar)4PorZn, where Por is the porphyrin dianion and Ar is a p-CH3Ph, Ph or p-ClPh substitutent on meso-positions of the macrocycle. Each Zn(II) butano- and benzoporphyrin undergoes two one-electron reductions to give a p-anion radical and dianion in CH2Cl2. In contrast, three reductions were observed for the benzoporphyrin derivatives in pyridine, the third of which is assigned as electron addition to a benzophlorin anion generated from the doubly reduced benzoporphyrin. Two overlapped one-electron oxidations were observed for the butanoporphyrins in CH2Cl2, a result not previously observed for any other zinc porphyrin. The electrochemically measured HOMO–LUMO gap of the benzoporphyrins ranges from 1.89 to 1.90 V in CH2Cl2 and from 1.93 to 1.95 V in pyridine. Both values are smaller than the gaps of butanoporphyrins at 2.11–2.13 V in CH2Cl2 and 2.07–2.09 V in pyridine.
关键词： spectroelectrochemistry,electrochemistry,substituent effect,synthesis,porphyrinoids
更新于2025-09-10 09:29:36