Journal
MOLECULES
Volume 27, Issue 19, Pages -Publisher
MDPI
DOI: 10.3390/molecules27196498
Keywords
triple-decker phthalocyaninates; conformation; UV-vis-NIR spectroscopy; simplified Tamm-Dancoff approximation; noncovalent interactions; reduced density gradient; quantum theory of atoms in molecules
Funding
- Ministry of Science and Higher Education of Russia [075-15-2020-779]
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This study investigates the conformational states of substituted lanthanide phthalocyaninates in solution, depending on the substituents, redox states, and solvents. It finds that the butoxy-substituted complex can switch between different conformational states, while the crown-substituted triple-decker complex maintains a staggered conformation regardless of external factors. Analysis of noncovalent interactions sheds light on the factors stabilizing certain conformers.
Double- and triple-decker lanthanide phthalocyaninates exhibit unique physical-chemical properties, particularly single-molecule magnetism. Among other factors, the magnetic properties of these sandwiches depend on their conformational state, which is determined via the skew angle of the phthalocyanine ligands. Thus, in the present work we report the comprehensive conformational study of substituted terbium(III) and yttrium(III) trisphthalocyaninates in solution depending on the substituents at the periphery of molecules, redox-states and nature of solvents. Conjunction of UV-vis-NIR spectroscopy and quantum-chemical calculations within simplified time-dependent DFT in Tamm-Dancoff approximation provided the spectroscopic signatures of staggered and gauche conformations of trisphthalocyaninates. Altogether, it allowed us to demonstrate that the butoxy-substituted complex behaves as a molecular switcher with controllable conformational state, while the crown-substituted triple-decker complex maintains a staggered conformation regardless of external factors. The analysis of noncovalent interactions within the reduced density gradient approach allowed to shed light on the nature of factors stabilizing certain conformers.
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