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Preferential Formation of Side‐Pocket‐Substituted Zinc Phthalocyanines Emitting Beyond 800 nm
Author(s) -
McKearney Declan,
Roberts Ryan J.,
Mitchell Devon,
Cheung Jeffrey C. F.,
Williams Vance E.,
Leznoff Daniel B.
Publication year - 2021
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/ejic.202100378
Subject(s) - chemistry , protonation , zinc , side chain , lithium (medication) , axial symmetry , chloride , ligand (biochemistry) , lithium chloride , phthalocyanine , crystallography , photochemistry , inorganic chemistry , ion , organic chemistry , polymer , medicine , biochemistry , receptor , structural engineering , engineering , endocrinology
A series of zinc (1,4,8,11,15,18,22,25‐octabutoxy)phthalocyanine ( 2 ) complexes that spontaneously form 5‐coordinate complexes with anionic axial ligands neutralized with side‐pocket cations, of the form Cation‐PcZnX (X=Cl, OAc; Cation=H + or Li + ), was synthesized and structurally characterized. The side‐pocket protonation of the axial‐chloride species pushed the emission maximum from 760 nm (for axial ligand‐free 2 ) to 826 nm, well into the NIR region. A 1D‐coordinated chain bridged by lithium and chloride atoms was isolated and structurally characterized, representing the first side‐pocket metalated PcM species. This preferential formation of axially substituted [PcZnX] − “ate” complexes and their sequestration of both protons and lithium cations, opens a new series of materials with unique structural and electronic properties. Furthermore, their ability to both absorb and emit in the NIR region makes them desirable for numerous applications.