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oai:figshare.com:article/34023322 2026-09-29T11:05:23Z category_1 category_915 category_21 category_272 category_873 category_39 category_45 portal_63 item_type_6 month_year_09_2026

H/F Substitution Regulates the Local Environment and Excited-State Relaxation of Tetrahedral Mn(II) Centers for Near-Unity Luminescence and X‑ray Scintillation Zhikai Qi (4669177) Zurong Wang (25136779) Xingxing Zhao (2792998) Nan Zhang (46264) Mengyu Yan (1410589) Xinxin Zhang (309944) Xian-Ming Zhang (1374327) Biophysics Physical Sciences not elsewhere classified Biotechnology Environmental Sciences not elsewhere classified Chemical Sciences not elsewhere classified Ecology Sociology ultralow detection limit photoluminescence quantum yield favorable operational stability dimensional hybrid chloride 9 lp mm 400 photons mev effective molecular strategy tea )< sub ftea )< sub 4 </ sub 2 </ sub local coordination environment 2 +</ sup tuning isolated mn work establishes h performance flexible x f substitution regulates local environment substitution strategy isolated mn flexible x tetrahedral mn f substitution resolution x high x unity luminescence subtly modulates state relaxation spatial resolution ray scintillators ray imaging radiative decay promising route nonradiative relaxation level regulation fluorinated analogue concurrent enhancement advancing high 42 ngy 1 %) Molecular-level regulation of isolated luminescent centers offers a promising route to efficient and flexible X-ray scintillators. Herein, we develop a hydrogen-to-fluorine (H/F) substitution strategy for tuning isolated Mn²⁺ emitters in a zero-dimensional hybrid chloride. The fluorinated analogue (FTEA)₂MnCl₄ (FTMC) is isostructural with the parent (TEA)₂MnCl₄ (TMC), while fluorination introduces F···Cl interactions (15.1%) and subtly modulates the local coordination environment of MnCl₄ units. This molecular modification nearly doubles the photoluminescence quantum yield from 49.8% for TMC to 97.5% for FTMC, enabled by concurrent enhancement of radiative decay and suppression of nonradiative relaxation. Notably, FTMC further exhibits a high X-ray scintillation light yield of 78,400 photons MeV^–1, an ultralow detection limit of 32.42 nGy s^–1, and favorable operational stability. Moreover, a flexible FTMC@PDMS scintillator enables high-resolution X-ray imaging with a spatial resolution of 11.9 lp mm^–1. This work establishes H/F substitution as an effective molecular strategy for regulating excited-state relaxation in isolated Mn²⁺ emitters and advancing high-performance flexible X-ray scintillators. 2026-09-29T00:00:00Z Text Journal contribution 10.1021/acs.inorgchem.6c04526.s001 https://figshare.com/articles/journal_contribution/H_F_Substitution_Regulates_the_Local_Environment_and_Excited-State_Relaxation_of_Tetrahedral_Mn_II_Centers_for_Near-Unity_Luminescence_and_X_ray_Scintillation/34023322 CC BY-NC 4.0