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Four boron-carrying molecules were synthesized and purified. These were found to be (a) relatively neutral with respect to the parent BF derivative and (b) functionalized by donor–acceptor groups resulting in a charge transfer within the molecule. The study discusses the steric effect and the influence of the substitution of the side rings on the surroundings of the boron atom. Electronic structures were characterized by real-space bonding indicators. Hirshfeld surface and energy frameworks tools were applied to examine the crystal packing features.

Symmetric Fluoroborate and its Boron Modification: Crystal and Electronic Structures