title: Rigidifying fluorescent linkers by metal-organic framework formation for fluorescence blue shift and quantum yield enhancement.
abstract: We demonstrate that rigidifying the structure of fluorescent linkers by structurally constraining them in metal-organic frameworks (MOFs) to control their conformation effectively tunes the fluorescence energy and enhances the quantum yield. Thus, a new tetraphenylethylene-based zirconium MOF exhibits a deep-blue fluorescent emission at 470 nm with a unity quantum yield (99.9 ± 0.5%) under Ar, representing ca. 3600 cm(-1) blue shift and doubled radiative decay efficiency vs the linker precursor. An anomalous increase in the fluorescence lifetime and relative intensity takes place upon heating the solid MOF from cryogenic to ambient temperatures. The origin of these unusual photoluminescence properties is attributed to twisted linker conformation, intramolecular hindrance, and framework rigidity.
authors.affiliation: Department of Chemistry, Texas A&M University , College Station, Texas 77843, United States.
authors.forename: Zhangwen
authors.initials: Z
authors.lastname: Wei
authors.forename: Zhi-Yuan
authors.initials: ZY
authors.lastname: Gu
authors.forename: Ravi K
authors.initials: RK
authors.lastname: Arvapally
authors.forename: Ying-Pin
authors.initials: YP
authors.lastname: Chen
authors.forename: Roy N
authors.initials: RN
authors.lastname: McDougald
authors.forename: Joshua F
authors.initials: JF
authors.lastname: Ivy
authors.forename: Andrey A
authors.initials: AA
authors.lastname: Yakovenko
authors.forename: Dawei
authors.initials: D
authors.lastname: Feng
authors.forename: Mohammad A
authors.initials: MA
authors.lastname: Omary
authors.forename: Hong-Cai
authors.initials: HC
authors.lastname: Zhou