Models for the Photosynthetic Reaction Center: Preparation, Spectroscopy, and Crystal and Molecular Structures of Cofacial Bisporphyrins Linked by cis-1,2- and trans-1,2-Ethene Bridges and of 1,1-Carbinol-Bridged Bisporphyrins

Senge, Ma­thias O.; Vicente, M. G. H.; Gerzevske, Kevin R.; Forsyth, Timothy P.; Smith, Kevin M.

doi:10.1021/ic00103a006

Cited by 70 publications

(29 citation statements)

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“…Crystals 2017, 7, 23 2 of 24 we do not include porphyrin derivatives and related compounds such as corrins, chlorins, phthalocyanines, metal-organic frameworks (MOFs) and covalent organic frameworks (COFs).…”

Section: Porphine the Parent Compoundmentioning

confidence: 99%

“…Factors important in optimizing porphyrin semiconducting properties include the planarity of the macrocycle, and its parallelism with others in the structure. When discussing electronic properties, it is important to differentiate among different structural regimes, [7,22,23]. Peripheral substituents are omitted for clarity.…”

Section: Electronic Properties As Related To Structurementioning

confidence: 99%

“…Crystals 2017, 7, 23 15 of 24 particular interest is the polymeric compound [Fe III (TPP)(ImPhO)]∞, where Im = imidazole and Ph = phenyl, and ImPhO is the composite axial ligand linking the macrocycles. This compound, which crystallizes in the non-centrosymmetric space group Pna21, is expected to have a permanent dipole moment parallel with the c-axis.…”

Section: Ferroelectric Porphyrinsmentioning

confidence: 99%

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Structural Aspects of Porphyrins for Functional Materials Applications

2017

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Porphyrinic compounds comprise a diverse group of materials which have in common the presence of one or more cyclic tetrapyrroles known as porphyrins in their molecular structures. The resulting aromaticity gives rise to the semiconducting properties that make these compounds of interest for a broad range of applications, including artificial photosynthesis, catalysis, molecular electronics, sensors, non-linear optics, and solar cells. In this brief review, the crystallographic attributes of porphyrins are emphasized. Examples are given showing how the structural orientations of the porphyrin macrocycle, and the inter-porphyrin covalent bonding present in multiporphyrins influence the semiconducting properties. Beginning with porphine, the simplest porphyrin, we discuss how the more complex structures that have been reported are described by adding peripheral substituents and internal metalation to the macrocycles. We illustrate how the conjugation of the π-bonding, and the presence of electron donor/acceptor pairs, which are the basis for the semiconducting properties, are affected by the crystallographic topology.

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Section: Porphine the Parent Compoundmentioning

confidence: 99%

Section: Electronic Properties As Related To Structurementioning

confidence: 99%

Section: Ferroelectric Porphyrinsmentioning

confidence: 99%

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Structural Aspects of Porphyrins for Functional Materials Applications

2017

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“…(44) was subjected to the McMurry reaction (TiCl 3 , Zn-Cu), the unexpected bis-porphyrinylcarbinol (45) was obtained in 61% yield [38] (Scheme 16). Figure 1 shows the X-ray structure of this unexpected product in which the two macrocycles form a skewed structure with a 77 angle between the two nitrogen planes [39]. A possible mechanism for the anomalous formation of the bis-porphyrinylcarbinol (45) is shown in Scheme 17, with the main uncertainty being the dashedline ligands on the titanium ion.…”

Section: From β-Formylporphyrinsmentioning

confidence: 99%

“…Surprisingly, the cis isomers predominated [39] for both the nickel(II) and copper(II) products; McMurry reactions usually provide trans alkene isomers [40]. It was rationalized that the cis isomers were preferred in the metalloporphyrin coupling reactions because of the πÀπ aggregation tendencies of metalloporphyrins [41][42][43][44].…”

Section: From Meso-formyl-and Meso-formylvinylporphyrinsmentioning

confidence: 99%

The McMurry Reaction in Porphyrinoid Chemistry

Smith

2013

Topics in Heterocyclic Chemistry

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The McMurry reaction, first reported in 1974, is an organometallic coupling reaction of aldehydes and ketones, to give alkenes, that relies upon the use of low-valent titanium; the reactive titanium species is obtained from titanium (III) or titanium(IV) chloride and an in situ reducing agent. The first application of the McMurry reaction to polypyrrole chemistry took place in 1986 with the first synthesis of the (2,0,2,0)-porphyrin isomer, porphycene. Since then, numerous macrocyclization reactions of polypyrrole (and other heteroaromatic) compounds have been described, and many new molecules have been reported. Peripheral carbonyl substituents on metallo-porphyrins and -chlorins have been coupled to yield a plethora of bis-porphyrins, bis-chlorins, and their homo-and hetero-bimetallic complexes. Some porphyrin-chlorin systems have also been reported. Thus, this contemporary organometallic coupling reaction has been successfully applied to polypyrrole syntheses and substituent manipulations, and a large number of interesting new compounds have been obtained.

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Porphyrin Dimers Linked by Conjugated Butadiyne Bridges: Preparations, Spectra, Voltammetry and Reductive Spectroelectrochemistry of {[M(OEP)](μ-C₄)[M(OEP)]}(M₂≡H₄, Co₂, Ni₂, Cu₂, Zn₂, Pd₂, Pt₂, Co/Ni, Ni

Arnold

Heath

James

1999

J. Porphyrins Phthalocyanines

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A series of derivatives M 2 P 2 ( M 2 ≡ H 4, Co 2, Ni 2, Cu 2, Zn 2, Pd 2, Pt 2, Co / Ni , Ni / Cu , Ni / Zn ) of the ligand meso,meso′-bis(octaethylporphyrinyl)butadiyne has been prepared and characterized by 1 H NMR, FT Raman and visible absorption spectroscopies as well as by cyclic and a.c. voltammetry in CH 2 Cl 2 solution at 20 and −40 °C. The electronic spectra exhibit multiple Soret bands and the voltammetry reveals successive one-electron reductions indicating the accessibility of ‘mixed valence’ π-radical anions and π-dianions. Using in situ thin layer spectroelectrochemistry, the UV to near-IR spectra of [ M 2 P 2]1− and [ M 2 P 2]2− ( M as above) were recorded at ≤ −40 °C. Apart from the Co complexes (reduced at the metal ion), the bis(porphyrin) anions have spectra which include sharp, intense near-IR bands (ε = 50 000–200 000 M−1cm−1) at c. 4500 and 11 500 cm−1([ M 2 P 2]1−) and 9500 cm−1([ M 2 P 2]2−). An empirically constructed semiquantitative frontier orbital model explains the observed electronic absorption bands. Inter-porphyrin conjugation, mediated by the butadiyne bridge, is responsible for the Soret band multiplicity. The near-IR bands of the anions are assigned to long-axis polarized π → π* transitions within the newly occupied upper manifold of the two-porphyrin eight-orbital framework. The small comproportionation constants found for the diporphyrin monoanions contradict the usual assumption that electronically coupled dimers should have a large voltammetric separation between the first and second redox steps.

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Models for the Photosynthetic Reaction Center: Preparation, Spectroscopy, and Crystal and Molecular Structures of Cofacial Bisporphyrins Linked by cis-1,2- and trans-1,2-Ethene Bridges and of 1,1-Carbinol-Bridged Bisporphyrins

Cited by 70 publications

References 0 publications

Structural Aspects of Porphyrins for Functional Materials Applications

Structural Aspects of Porphyrins for Functional Materials Applications

The McMurry Reaction in Porphyrinoid Chemistry

Porphyrin Dimers Linked by Conjugated Butadiyne Bridges: Preparations, Spectra, Voltammetry and Reductive Spectroelectrochemistry of {[M(OEP)](μ-C₄)[M(OEP)]}(M₂≡H₄, Co₂, Ni₂, Cu₂, Zn₂, Pd₂, Pt₂, Co/Ni, Ni

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Models for the Photosynthetic Reaction Center: Preparation, Spectroscopy, and Crystal and Molecular Structures of Cofacial Bisporphyrins Linked by cis-1,2- and trans-1,2-Ethene Bridges and of 1,1-Carbinol-Bridged Bisporphyrins

Cited by 70 publications

References 0 publications

Structural Aspects of Porphyrins for Functional Materials Applications

Structural Aspects of Porphyrins for Functional Materials Applications

The McMurry Reaction in Porphyrinoid Chemistry

Porphyrin Dimers Linked by Conjugated Butadiyne Bridges: Preparations, Spectra, Voltammetry and Reductive Spectroelectrochemistry of {[M(OEP)](μ-C4)[M(OEP)]}(M2≡H4, Co2, Ni2, Cu2, Zn2, Pd2, Pt2, Co/Ni, Ni

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Porphyrin Dimers Linked by Conjugated Butadiyne Bridges: Preparations, Spectra, Voltammetry and Reductive Spectroelectrochemistry of {[M(OEP)](μ-C₄)[M(OEP)]}(M₂≡H₄, Co₂, Ni₂, Cu₂, Zn₂, Pd₂, Pt₂, Co/Ni, Ni