Modulation of Axial-Ligand Binding and Releasing Processes onto the Triazole-Bearing Nickel(II) Picket-Fence Porphyrins: Steric Repulsion versus Hydrogen-Bonding Effects

Juwon Oh, Hongsik Yoon, Young Mo Sung, Philjae Kang, Moon Gun Choi, Woo Dong Jang, Dongho Kim

Research output: Contribution to journalArticlepeer-review

4 Citations (Scopus)

Abstract

N-(p-Methoxycarbonylbenzyl) triazole (BTz) substituents have been introduced to Ni(II) porphyrins (NiPs), in which their modulated axial-coordination processes have been investigated. For this study, the two types of ligands, neutral pyridine versus anionic cyanide, were employed to investigate an effect of BTz substituents. The unique microenvironments given by the BTz substituents provided two different effects on the axial-coordination processes of NiPs on the ground and excited states: (1) steric shielding and (2) donation of hydrogen-bonding sites. The steric shielding diminished the binding affinity of pyridine, while the cooperation of hydrogen bonds extraordinarily strengthened the binding affinity of CN-. Interestingly, it was observed that the binding of CN- with the supporting of BTz substituents accompanied nonplanar distortion of NiPs. Such conformational change perturbed the electronic structure of NiPs, which gave rise to the modulation of coordination processes of NiPs in the excited state. As a consequence, photoinudced ligand binding and releasing processes of four- and six-coordinated NiPs were changed into the dominant photoinduced ligand releasing process. (Figure Presented).

Original languageEnglish
Pages (from-to)7053-7061
Number of pages9
JournalJournal of Physical Chemistry B
Volume119
Issue number23
DOIs
Publication statusPublished - 2015 Jun 11

All Science Journal Classification (ASJC) codes

  • Physical and Theoretical Chemistry
  • Surfaces, Coatings and Films
  • Materials Chemistry

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