Solid‐State Photoconversion of a Discrete Mixed Iodine(I) System to a 1D Polymer

Abstract The first example of a mixed halogen(I) complex ( 2 ), containing three distinct iodine(I) moieties ([N―I―N] + , O―I―N, and [O―I―O] − ) within the same structure, was synthesized with 4‐styrylpyridine (4‐stypy) and 3,4,5,6‐tetrafluorophthalate as the stabilizing Lewis bases. This complex was observed to be in equilibrium with its respective bis (OIN) complex ( 1a ), with isolated samples of 2 also being found to convert to 1a in solution. Upon UV irradiation of 2 , a single‐crystal‐to‐single‐crystal [2 + 2] cycloaddition reaction was observed, converting the discrete salt 2 to the 1D polymer 5 . Complex 5 retained all the iodine(I) moieties from prior to photoconversion and represents the first example of nondestructive photoconversion of a halogen(I) complex. To facilitate comparisons to 2 and 5 , several additional closely related iodine(I) complexes were synthesized, with the iodine(I) complexes characterized by NMR ( 1 H, 1 H‐ 15 N HMBC) and SCXRD, as well as by Raman and IR spectroscopy for 2 , 5 , and their close structural analogue 1a .