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Testing the Limits of the BOPHY Platform: Preparation, Characterization, and Theoretical Modeling of BOPHYs and Organometallic BOPHYs with Electron‐Withdrawing Groups at β‐Pyrrolic and Bridging Positions
Author(s) -
Zatsikha Yuriy V.,
Nemez Dion B.,
Davis Rebecca L.,
Singh Simarpreet,
Herbert David E.,
King Alex J.,
Ziegler Christopher J.,
Nemykin Victor N.
Publication year - 2017
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201702597
Subject(s) - chemistry , differential pulse voltammetry , adduct , cyclic voltammetry , ferrocene , electrochemistry , crystallography , photochemistry , organic chemistry , electrode
Several BOPHY derivatives with and without ferrocene fragments, and with electron‐withdrawing ester groups appended to the β‐pyrrolic positions have been prepared and characterized by NMR, UV/Vis near‐infrared (NIR), high‐resolution mass spectrometry, and fluorescence spectroscopy, as well as X‐ray crystallography. The redox properties of new BOPHYs were probed by electrochemical (cyclic and differential pulse voltammetry) and spectroelectrochemical methods. In an attempt to prepare BOPHY derivatives with a cyano group at the bridging position using a similar approach for BODIPY cyanation, adducts from the nucleophilic attack of the cyanide anion on the bridging position in BOPHY have been isolated and characterized by spectroscopic methods. Oxidation of such adducts, however, resulted in formation of either the starting BOPHYs, or partial extrusion of the BF 2 fragment from the BOPHY core, which was confirmed by spectroscopy and X‐ray crystallography. DFT and TDDFT calculations on all target materials correlate well with the experimental data, and suggest the dramatic reduction of the nitrogen atom basicity at the hydrazine bridge of the BOPHY upon introduction of the cyano group at the bridging‐carbon atom.