Modulating Mechanochromic Luminescence Quenching of Alkylated Iodo Difluoroboron Dibenzoylmethane Materials

William A. Morris, Michal Sabat, Tristan Butler, Christopher A. Derosa, Cassandra L. Fraser

Research output: Contribution to journalArticlepeer-review

34 Scopus citations


Difluoroboron β-diketonate compounds exhibit solid-state luminescence phenomena. Among these are reversible mechanochromic luminescence (ML), aggregation induced emission (AIE), and mechanochromic luminescence quenching (MLQ). These properties can be tuned by alterations to the molecular structure. Dyes with varying halide substituents exhibit tunable ML, MLQ, and solid-state emission with high quantum yields. A series of difluoroboron dibenzoylmethane (BF2dbm) dyes with iodide and alkoxyl substituents (BF2dbm(I)OR) were synthesized where R = CH3 (C1), C5H11 (C5), C6H13 (C6), C12H25 (C12), and C18H37 (C18)). The 4-iodo parent compound BF2dbm(I) (H) was made for comparison. By keeping the heavy atom static, the dependence of ML properties on alkyl chain length was probed. The hydrogen derivative is only weakly emissive as a solid and exhibited minimal mechanoresponsive behavior. In contrast, alkoxy dyes exhibited tunable ML and MLQ properties depending on the length of the alkyl chain. Longer chain dyes corresponded to smaller singlet triplet energy gaps, greater triplet emission enhancement (77 K), and longer recovery times after smearing under ambient conditions. Shorter chain dyes have a much greater affinity for the ordered emissive state, as confirmed by atomic force microscopy (AFM). Powder X-ray diffraction (XRD) was performed on pristine dye powders as well as drop-cast films to gauge crystallinity in various forms. Single crystal XRD analysis of the H and C5 dyes revealed significant differences in crystal packing and π-π stacked dimers for dyes bearing alkyl chains and dyes without alkyl chains. Unique I-I and F-π close interactions were discovered in the dye crystals.

Original languageEnglish (US)
Pages (from-to)14289-14300
Number of pages12
JournalJournal of Physical Chemistry C
Issue number26
StatePublished - Jul 7 2016

Bibliographical note

Funding Information:
We thank the National Science Foundation (NSF CHE- 1213915) for support for this research and Professor Carl O. Trindle for guidance and helpful discussions concerning computational studies and methods.

Publisher Copyright:
© 2016 American Chemical Society.

Copyright 2016 Elsevier B.V., All rights reserved.


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