Efficient and Stable Thin‐Film Luminescent Solar Concentrators Enabled by Near‐Infrared Emission Perovskite Nanocrystals

A novel triphenylphosphine (TPP) treatment strategy was developed to prepare the near‐infrared emission CsPbI₃ nanocrystal (NC)‐polymer composite thin‐film luminescent solar concentrators (LSCs) featuring high absolute photoluminescence quantum yield (PLQY), low reabsorption, and high stability. The PL emission of the LSCs is centered at about 700 nm with 99.4±0.4 % PLQY and narrow full width at half maximum (FWHM) of 75 meV (30 nm). Compared with LSCs prepared with classic CsPbI₃ NCs, the stability of the LSCs after TPP treatments has been greatly improved, even after long‐term (30 days) immersion in water and strong mercury‐lamp irradiation (50 mW cm^?2). Owing to the presence of lone‐pair electrons on the phosphorus atom, TPP is also used as a photoinitiator, with higher efficiency than other common photoinitiators. Large‐area (ca. 75 cm²) infrared LSCs were achieved with a high optical conversion efficiency of 3.1 % at a geometric factor of 10.     

含有三苯胺-三唑双极性单元的橙红光阳离子型铱(Ⅲ)配合物的合成及在LEDs中的应用

以2-萘基吡啶(npy)为主配体, N,N-二苯基-4-[4-苯基-5-(吡啶-2-基)-4H-1,2,4-三唑-3-基]苯胺(DPPTA)为辅助配体, 合成了含有三苯胺-三唑双极性结构单元的橙红光阳离子型有机铱(Ⅲ)配合物[(npy)₂Ir(DPPTA)]PF₆. 该配合物的热分解温度高达345 ℃, 从20 ℃升温到100 ℃时, 相对发光强度衰减28.0%, 发光颜色稳定. 其所含的双极性结构单元使其能有效地吸收GaN芯片的蓝光(λ_em,max=455 nm), 进而可被蓝光高效激发. 以GaN蓝光芯片作为激发光源, [(npy)₂Ir(DPPTA)]PF₆为下转换发光材料, 可以制得橙红光LEDs; 进一步与黄光材料Y₃Al₅O₁₂∶Ce³⁺(YAG:Ce³⁺)联用, 可以制得高效的中性白光和暖白光LEDs.     

Widely Electronically Tunable 2,6-Disubstituted Dithieno[1,4]thiazines—Electron-Rich Fluorophores Up to Intense NIR Emission

2,6-Difunctionalized dithieno[1,4]thiazines were efficiently synthesized by (pseudo)five- or (pseudo)three-component one-pot processes based on lithiation-electrophilic trapping sequences. As supported by structure–property relationships, the thiophene anellation mode predominantly controls the photophysical and electrochemical properties and the electronic structures (as obtained by DFT calculations). From molecular geometries and redox potentials to fluorescence quantum yields in solution, the interaction of the dithieno[1,4]thiazine-core with the substituents causes striking differences within the series of regioisomers. Most interestingly, strong acceptors introduced in anti–anti dithieno[1,4]thiazines nearly induce a planarization of the ground-state geometry and a highly intense NIR fluorescence (Φ_F=0.52), whereas an equally substituted syn–syn dithieno[1,4]thiazine exhibits a much stronger folded molecular structure and fluoresces poorly (Φ_F=0.01). In essence, electrochemical and photophysical properties of dithieno[1,4]thiazines can be tuned widely and outscore the compared phenothiazine with cathodically shifted oxidation potentials and redshifted and more intense absorption bands.     

拉伸诱导的自修复铂配合物薄膜的发光变化

通过接枝含醛基的铂配合物Pt(N^C^N)Cl(N^C^N=1,3-二吡啶基苯)到聚二甲基硅氧烷(PDMS)骨架上,制备了一种弹性橙红色薄膜(PDMS-PtL1)。PDMS-PtL1薄膜具有很好的拉伸性(高达1500%的应变),并表现出较好的室温自修复性能。此外,PDMSPt L1薄膜表现出有趣的拉伸诱导的发光变化,拉伸后可以检测到单分子态铂配合物的~3π-π*发射。该弹性薄膜有效避免了铂配合物发光淬灭的现象,并且实现了外力诱导的发射态转换。     

一种用于选择性检测苯乙烯的Zn-MOFs发光传感器

在溶剂热条件下合成了一种新型金属有机框架（MOF）{[Zn₂（tyia）₂（H₂O）₂]·H₂O}_n（1）,其中H₂tyia为5-（1H-1,2,4-三唑-1-基）间苯二甲酸。运用X射线单晶衍射分析其结构,通过元素分析、粉末X射线衍射、热重分析、固体荧光分析等手段对配合物1进行表征,研究了其与有机小分子相互作用的荧光特性。结果表明其能够对低浓度苯乙烯迅速做出反应,最低识别浓度为1.06 mmol·L^-1。此外,还对其传感机制进行了研究。     

氯代芳香羧酸与联吡啶配体构筑的四种稀土配合物的晶体结构、热分析和荧光性质

利用2种氯代芳香羧酸（3,4-二氯苯甲酸和3,5-二氯苯甲酸,分别简写为3,4-HDClBA和3,5-HDClBA）与5,5''-二甲基-2,2''-联吡啶（5,5''-DM-2,2''-bipy）配体在溶剂热或常温反应的条件下成功地合成了4种稀土配合物[Ln₂（5,5''-DM-2,2''-bipy）₂（3,4-DClBA）₆（H₂O）（C₂H₅OH）]（Ln=Sm（1）,Eu（2））和[Ln（5,5''-DM-2,2''-bipy）（3,5-DClBA）₃]₂（Ln=Sm（3）,Eu（4））。配合物1和2是同构的,每个中心离子是八配位的扭曲四方反棱柱的几何构型,分子与分子之间通过C-H…Cl氢键和π-π堆积作用形成二维的超分子结构。配合物3的几何构型为九配位的单帽四方反棱柱体,分子与分子之间通过不同的π-π堆积作用形成二维的超分子结构。利用热重红外联用技术研究了配合物1~4的热稳定性和热分解机理。对配合物2和4进行了荧光以及荧光寿命研究,结果表明2个配合物都能发射Eu³⁺离子的特征荧光。     

一维镉(Ⅱ)和镍(Ⅱ)配位聚合物的合成、晶体结构、荧光及磁性质（英文）

在水热条件下,用联苯类四羧酸配体(H4L)和菲咯啉(phen)分别与CdCl2·H2O和NiCl2·6H2O反应,合成了2个具有一维链结构的配合物{[M2(μ3-L)(phen)3]·5H2O}n(M=Cd(1),Ni(2)),并对其结构、荧光和磁性质进行了研究。结构分析结果表明2个配合物是异质同心的,属于正交晶系,Pbca空间群。2个配合物具有一维链结构,而且这些链通过O-H…O氢键作用进一步形成了二维超分子网络。研究表明,配合物1在室温下能发出蓝色荧光,配合物2中相邻Ni?髤离子间存在铁磁相互作用。     

含有3,4-吡唑二甲酸的锌(Ⅱ)配合物:合成、结构和荧光性质（英文）

3,4-吡唑二甲酸(H3pdc)与Zn(NO3)2·6H2O在不同的条件下反应制得了2个新的配合物:[Zn(H2pdc)2(H2O)2]·2H2O(1)和[Zn2(Hpdc)2(H2O)6]·2H2O(2)。X射线衍射分析表明,1和2分别是单核和双核结构。H3pdc部分脱质子后的阴离子配体在1和2中采用的是N,O-螯合(H2pdc-)以及μ2-κN,O∶κN桥联(Hpdc2-)配位模式。在这2个配合物中,相邻的零维组分通过分子间氢键(O-H…O,N-H…O和C-H…O)作用形成三维超分子结构。此外我们还研究了配合物1和2的热稳定性和荧光性能。     

Enzyme‐Triggered Disassembly of Perylene Monoimide‐based Nanoclusters for Activatable and Deep Photodynamic Therapy

Photodynamic therapy (PDT) exhibits great potential for cancer therapy, but still suffers from nonspecific photosensitivity and poor penetration of photosensitizer. Herein, a smart perylene monoimide‐based nanocluster capable of enzyme‐triggered disassembly is reported as an activatable and deeply penetrable photosensitizer. A novel carboxylesterase (CE)‐responsive tetrachloroperylene monoimide (P1) was synthesized and assembled with folate‐decorated albumins into a nanocluster ( FHP ) with a diameter of circa 100 nm. Once P1 is hydrolyzed by the tumor‐specific CE, FHP disassembles into ultrasmall nanoparticles (ca. 10 nm), facilitating the deep tumor penetration of FHP . Furthermore, such enzyme‐triggered disassembly of FHP leads to enhanced fluorescence intensity (ca. 8‐fold) and elevated singlet oxygen generation ability (ca. 4‐fold), enabling in situ near‐infrared fluorescence imaging and promoted PDT. FHP permits remarkable tumor inhibition in vivo with minimal side effects through imaging‐guided, activatable, and deep PDT. This work confirms that this cascaded multifunctional control through enzyme‐triggered molecular disassembly is an effective strategy for precise cancer theranostics.     

Crosslink-Enhanced Emission Effect on Luminescence in Polymers: Advances and Perspectives

The crosslink-enhanced emission effect was first proposed to explore the strong luminescence of nonconjugated polymer dots possessing only either non-emissive or weakly emissive sub-luminophores. Interesting phenomena in recent research indicate such enhancement caused by extensive crosslinking appears in diverse luminescent polymers with sub-luminophores (electron-rich heteroatomic moieties) or luminophores (conjugated π domains). This enhancement can promote the emission from nonluminous to luminous, from weakly luminous to strongly luminous, and even convert the pathway of radiative transitions. The concept of the crosslink-enhanced emission effect should be updated and extended to an in-depth spatial effect, such as electron overlap and energy splitting in confined domains by effective crosslinking, more than initial immobilization. This Minireview outlines the development of the crosslink-enhanced emission effect from the perspective of the detailed classification, inherent mechanism and applicable systems. An outlook on the further exploration and application of this theory are also proposed.