Tunable room temperature phosphorescence and energy transfer in ratiometric co-crystals

Zhou, Bo; Zhao, Qihang; Tang, Longchang; Yan, Dongpeng

doi:10.1039/d0cc02730h

Cited by 100 publications

(67 citation statements)

References 34 publications

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“…olecular luminescent materials have attracted increasingly widespread attention due to their extensive applications in illumination resources, light-emitting diodes (LEDs), and biological imaging among many others [1][2][3][4][5][6][7][8][9][10][11][12][13][14][15][16][17][18][19][20] . It is well known that the luminescence of molecular systems is usually sensitive to temperature, such that increasing temperature tends to provoke with intensification of molecular rotation and lattice vibration in chromophores, thereby facilitating the universal thermal-quenching (TQ) effect 21,22 .…”

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confidence: 99%

Wide range zero-thermal-quenching ultralong phosphorescence from zero-dimensional metal halide hybrids

et al. 2020

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Materials with ultralong phosphorescence have wide-ranging application prospects in biological imaging, light-emitting devices, and anti-counterfeiting. Usually, molecular phosphorescence is significantly quenched with increasing temperature, rendering it difficult to achieve high-efficiency and ultralong room temperature phosphorescence. Herein, we spearhead this challenging effort to design thermal-quenching resistant phosphorescent materials based on an effective intermediate energy buffer and energy transfer route. Co-crystallized assembly of zero-dimensional metal halide organic-inorganic hybrids enables ultralong room temperature phosphorescence of (Ph4P)2Cd2Br6 that maintains luminescent stability across a wide temperature range from 100 to 320 K (ΔT = 220 °C) with the room temperature phosphorescence quantum yield of 62.79% and lifetime of 37.85 ms, which exceeds those of other state-of-the-art systems. Therefore, this work not only describes a design for thermal-quenching-resistant luminescent materials with high efficiency, but also demonstrates an effective way to obtain intelligent systems with long-lasting room temperature phosphorescence for optical storage and logic compilation applications.

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confidence: 99%

Wide range zero-thermal-quenching ultralong phosphorescence from zero-dimensional metal halide hybrids

et al. 2020

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“…Packing pattern of the organic phosphors can also be inflected by cocrystallizing them with different molar ratios of the same coformer, which plays an important role in PL properties by modifying electronic couplings, band structures, and exciton behaviors. [48,49] Recently, Alam et al have published a paper titled "Two are Better Than One" and have reported a series of N,N-dimethylaniline doped pure organic quaternary phosphonium bromide salts crystals, which generates afterglow for up to 7 h. [35] The cocrystals with RTP, are mostly bonded with electron transfer features, which can be ascribed to the strong intermolecular interactions (hydrogen/halogen bonds, ionic bond, π-π stacking and so on, Figure 2) that play as the main driving forces for the formation of cocrystals when a strong acceptor molecule assembles with a suitable donor molecule. Almost all the reported cocrystals with RTP have the donor molecules with heteroatoms and acceptor molecules with halogen atoms (Figures 3 and 4), and halogen bonding is the main driving force for their cocrystal formation.…”

Section: Design Perspectives For Organic Cocrystals With Rtpmentioning

confidence: 99%

Section: Design Perspectives For Organic Cocrystals With Rtpmentioning

confidence: 99%

Recent Advances of Cocrystals with Room Temperature Phosphorescence

Singh

Liu

et al. 2021

Advanced Optical Materials

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bioavailability, etc.) can be modified by cocrystallization with coformers. Beyond active pharmaceutical ingredients, cocrystallization is being extensively or has also been established as a effective technique to change or improve the photoluminescence (PL) properties of the organic materials, [2][3][4][5][6] along with to discover the structure-property associations at a molecular level. [7,8] Room temperature phosphorescence (RTP), continuously one of the dynamic research fields in science and technology currently, due to extensive applications in various fields such as optoelectronics, [9] photomedicine, [10,11] sensing, [12,13] bioimaging, [14][15][16] encryption, [17,18] lighting, [19] logic gates, [20] and so on. The luminescence characteristics (such as lifetime, intensity and color) of RTP, can be effectively modified through molecular crystal engineering. [21][22][23] Phosphorescence is a radiative relaxation of excitons from the excited state having different spin multiplicity (triplet excited states) to ground state (Figure 1). Based on the quantum mechanics theory, [24] the transition between singlet to triplet is forbidden, that is, electrons cannot jump from singlet to triplet states. Generally, in all organic molecules ground states (S 0 ) are singlets; therefore, the emissive transition of singlet excitons from S 1 (lowest singlet excited state) to the S 0 is theoretically allowed, which is a fast process (fluorescence) with a very short lifetime (generally in nanoseconds). Contrary, the emissive transition of triplet excitons from T 1 (lowest triplet excited state) to the S 0, that is, phosphorescence exhibits comparatively much longer lifetime (microseconds to hours, may be in days), is theoretically forbidden and it is highly concerned with external conditions too, such as heat and oxygen (nonradiative transition). Therefore, for pure organic molecules with energy gaps (between S 1 and T 1 ) >0.5 eV, it is hard to achieve RTP, and the persistent RTP is even rare (typically lifetime > 0.1 s). Besides these, purely organic RTP materials have special features and advantages such as excellent molecular designable capability with modified properties, flexibility, being light weight, good stability, and processability, low toxicity, reduced manufacturing costs and compatibility with a vast range of substrates.Although, to date, many effective approaches, including design principles (based on halogen bonding, [25][26] H-aggregation, [16,27] and n-π transition [28,29] ) and RTP enhancement strategies Organic phosphorescent materials have attracted wide attention in recent years owing to their opportunities in various functional applications. Through appropriate molecular design strategies and synthetic perspectives to modulate their weak spin-orbit coupling, highly active triplet excitons, and ultrafast deactivation, the organic phosphors can be endowed with long-lived room temperature phosphorescence (RTP) characteristics. Organic cocrystals constructed by noncovalent intermolecular interactions (hyd...

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“…Self‐assembly in molecular systems has inspired a new generation of supramolecular materials with applications ranging from solid‐state luminescent materials[ 1 , 2 , 3 ] to molecular recognition and binding. [ 4 , 5 , 6 ] Among the developments, self‐associating amphiphiles (SSAs) are emerging as a new motif in the design of supramolecular macromolecular materials.…”

Section: Introductionmentioning

confidence: 99%

Squaramide‐Based Self‐Associating Amphiphiles for Anion Recognition

et al. 2021

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The synthesis and characterisation of two novel self‐assembled amphiphiles (SSAs) SQS‐1 and SQS‐2 are reported. Both compounds, based on the squaramide motif, were fully soluble in a range of solvents and were shown to undergo self‐assembly through a range of physical techniques. Self‐assembly was shown to favour the formation of crystalline domains on the nanoscale but also fibrillar film formation, as suggested by SEM analysis. Moreover, both SQS‐1 and SQS‐2 were capable of anion recognition in DMSO solution as demonstrated using 1H NMR and UV/Vis absorption spectroscopy, but displayed lower binding affinities for various anions when compared against other squaramide based receptors. In more competitive solvent mixtures SQS‐1 gave rise to a colourimetric response in the presence of HPO42− that was clearly visible to the naked eye. We anticipate that the observed response is due to the basic nature of the HPO42− anion when compared against other biologically relevant anions.

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Tunable room temperature phosphorescence and energy transfer in ratiometric co-crystals

Abstract: Color-tunable green and yellow room temperature phosphorescence is realized through a ratiometric co-crystal strategy.

Cited by 100 publications

References 34 publications

Wide range zero-thermal-quenching ultralong phosphorescence from zero-dimensional metal halide hybrids

Wide range zero-thermal-quenching ultralong phosphorescence from zero-dimensional metal halide hybrids

Recent Advances of Cocrystals with Room Temperature Phosphorescence

Squaramide‐Based Self‐Associating Amphiphiles for Anion Recognition

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