Solid-State Polycondensation via Ionic-to-Covalent Bond Transformation to Control Polymer Structure: Preparation of Porphyrin-Based Ladder Polymer

Suzuki, Masato; Yokota, Kazumasa; Tsuchida, Hiroe; Yamoto, Kazuhisa; Nagata, M.; Matsuoka, Shin‐ichi; Takagi, Koji; Johmoto, Kohei; Uekusa, Hidehiro

doi:10.1021/acsmacrolett.5b00013

Cited by 4 publications

(3 citation statements)

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“…A common structural feature among the BP crystals we discussed earlier is the near face-to-face arrangement of alternating ionic tectons in highly coherent columns propagating along the primary growth direction of the crystals (Figure ). Such ordered geometrical arrangement of porphyrin macrocycles was not observed in the few crystal structures of BPs prepared by others. ,− Shelnutt and Medforth, for example, determined that the crystal structure of nanosheets composed of ZnTSPP and Sn(IV)-tetra( N -methyl-4-pyridiniumyl) porphyrin exhibited severe slipped π–π stacking of the synthons in the crystal framework . This arrangement resulted in no significant electronic interactions between the porphyrin ionic dimers, and the material was found to not be photoconductive .…”

Section: Structure Morphology and Spectroscopymentioning

confidence: 93%

“…The length of the alkyl substituents on the monomers significantly influenced the degree of misalignment of the ionic macrocycles. Slipped layers of porphyrin synthons were also observed in the triclinic crystals formed from meso-tetrakis(4-carboxyphenyl)porphyrin, TCPP 4– , and meso -tetrakis[4-(pyridiniummethyl)phenyl]porphyrin, TPyPP 4+ . In the crystals composed of a 1:2 ratio of free-base and zinc(II) substituted porphyrin tetrathiafulvalenes, the porphyrin chromophores were offset and bridged by the tetrathiafulvalene moieties …”

Section: Structure Morphology and Spectroscopymentioning

confidence: 93%

“…Slipped layers of porphyrin synthons were also observed in the triclinic crystals formed from meso-tetrakis(4-carboxyphenyl)porphyrin, TCPP 4− , and meso-tetrakis [4-(pyridiniummethyl)phenyl]porphyrin, TPyPP 4+ . 72 In the crystals composed of a 1:2 ratio of free-base and zinc(II) substituted porphyrin tetrathiafulvalenes, the porphyrin chromophores were offset and bridged by the tetrathiafulvalene moieties. 73 Significant structural changes can potentially occur in the BP crystals when they are heated due to the loss of the water molecules which reside within the crystalline channels 49 or by chemical decomposition.…”

Section: ■ Synthesis and Controlled Growthmentioning

confidence: 99%

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A Systematic Approach toward Designing Functional Ionic Porphyrin Crystalline Materials

Mazur

Hipps

2018

J. Phys. Chem. C

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Synthetic ionic porphyrin self-assembled structures possess remarkable optoelectronic properties that are useful for energy and sensor related technological application, and there is a continued interest in tailoring their molecular structure and interactions in order to control their various functions. Central to these efforts is the fundamental understanding of the structure, the chemical and physical properties, and the relationship between the structural organization of the chromophores and their functions. In this Feature Article, we demonstrate the capability of a nucleation and growth algorithm to reproducibly synthesize nano- to millimeter size single crystals of several different ionic binary porphyrin (BP) systems under chemically controlled conditions. Single crystal X-ray diffraction analysis, morphology, sensing, and mechanical measurements are presented. UV–vis and X-ray photoelectron spectroscopy of these materials is also discussed. The crystalline porphyrin assemblies have varying degrees of dark conductivity (depending on their chemical and structural composition) but all appear to be sensitive to light; i.e., they absorb radiation and become conductive and/or persistently photoconductive (PPC). In addition, some of these crystalline porphyrins show persistent ion beam induced conductivity. This rich photo and ion response provides opportunities for the selective light control of these semiconductors. Exposure of the BP crystals to small gas molecules such as O2 strongly modifies their photocurrent in sensing experiments. The range of the Young’s modulus values extracted from nanoindentation experiments indicates that the BP crystals have a Young’s modulus intermediate between “soft” polymers and composite materials, making them excellent candidates for deformable optoelectronic devices. Both the experimental photoconductive and mechanical properties of the porphyrin self-assembled structures can be correlated with their molecular organization and morphology. In addition, quantum mechanical calculations provide the electronic band structure and the density of states and help explain experimental prompt photoconductivity measurements. Theory was also used to develop strategies for precise manipulation of the photoresponse of the BP crystals by selective structure modification. This work shows that combining the results from structural and theoretical studies and correlating them with electronic and optoelectronic properties can assist in engineering highly organized functional materials from organic π-conjugated molecules.

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