The design of white‐light phosphors is attractive in solid‐state lighting (SSL) and related fields. A new strategy in obtaining white light emission (WLE) from dual‐way photon energy conversion in a series of dye@MOF (LIFM‐WZ‐6) systems is presented. Besides the traditional UV‐excited one‐photon absorption (OPA) pathway, white‐light modulation can also be gained from the combination of NIR‐excited green and red emissions of MOF backbone and encapsulated dyes via two‐photon absorption (TPA) pathway. As a result, down‐conversion OPA white light was obtained for RhB+@LIFM‐WZ‐6 (0.1 wt %), BR‐2+@LIFM‐WZ‐6 (2 wt %), and APFG+@LIFM‐WZ‐6 (0.1 wt %) samples under 365 nm excitation. RhB+@LIFM‐WZ‐6 (0.05 wt %), BR‐2+@LIFM‐WZ‐6 (1 wt %) and APFG+@LIFM‐WZ‐6 (0.05 wt %) exhibit up‐conversion TPA white light under the excitation of 800, 790, and 730 nm, respectively. This new WLE generation strategy combines different photon energy conversion mechanisms together.
Excited-state
intramolecular proton transfer (ESIPT) molecules
demonstrating specific enol-keto tautomerism and the related photoluminescence
(PL) switch have wide applications in displaying, sensing, imaging,
lasing, etc. However, an ESIPT-attributed coordination polymer showing
alternative PL between thermally activated fluorescence (TAF) and
long persistent luminescence (LPL) has never been explored. Herein,
we report the assembly of a dynamic Cd(II) coordination polymer (LIFM-101)
from the ESIPT-type ligand, HPI2C (5-(2-(2-hydroxyphenyl)-4,5-diphenyl-1H-imidazol-1-yl)isophthalic acid). For the first time, TAF
and/or color-tuned LPL can be achieved by controlling the temperature
under the guidance of ESIPT excited states. Noteworthily, the twisted
structure of the HPI2C ligand in LIFM-101 achieves an effective mixture
of the higher-energy excited states, leading to ISC (intersystem crossing)/RISC
(reverse intersystem crossing) energy transfer between the high-lying
keto-triplet state (T
n
(K*)) and the first
singlet state (S1(K*)). Meanwhile, experimental and theoretical
results manifest the occurrence probability and relevance among RISC,
ISC, and internal conversion (IC) in this unique ESIPT-attributed
coordination polymer, leading to the unprecedented TAF/LPL switching
mechanism, and paving the way for the future design and application
of advanced optical materials.
Scheme 2. Deprotanation reaction of Sensor 1 in presence of OH − . Scheme 3. The proposed mechanism of interaction between Sensor 2, CN -, and Fanion.Scheme 4. A naphthalimide-based fluorescent Sensor 3 for the reversible detection of CNand TFA.
Organic LPL (long-persistent luminescence) materials have sparked extensive research interest due to the ultralong-lived triplet states. Although numerous organic LPL materials have been reported, most of the triplet emission was static and monotonous. Therefore, LPL materials with dynamic triplet emission are urgently required. A triamino-s-triazine derivative 1 with dynamic LPL was fabricated. The single-crystal structure shows that the abundant intermolecular interactions and small free volume restrict the molecular motion and avoid the quenchers. Spectral and theoretical calculations upheld the existence of multiple excited states in 1, and the migration of electrons between multiple excited states is very sensitive to external stimuli. By modulating the stimulus, the residence of electrons in different triplet states can be manipulated to achieve RGB LPL. Importantly, blue LPL was achieved by manipulating the anti-Kasha emission. And the red LPL can still be observed at high temperature.
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