CN116063242A - 一种近红外发光的手性Cu6团簇材料及其在夜视成像中的应用 - Google Patents
一种近红外发光的手性Cu6团簇材料及其在夜视成像中的应用 Download PDFInfo
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Abstract
本发明公开了一种近红外发光的手性铜团簇材料及其在夜视成像中的应用,属于配位化学和纳米材料的交叉领域。该手性铜团簇对映体以手性配体(S/R)‑4‑异丙基噻唑烷‑2‑硫酮(简写为:R/S‑iptt)为保护配体,通过简单的一步反应合成得到。该对映体团簇的化学式为:C36H60Cu6N6S12,简写为:R/S‑CS2,属于单斜晶系,空间群为手性空间群C2,S‑CS2:a=23.6472Å,b=16.7178Å,c=13.7830Å,α=90˚,β=96.039˚,γ=90˚,V=5418.6Å3;R‑CS2:a=23.6598Å,b=16.7141Å,c=13.7523Å,α=90˚,β=95.994˚,γ=90˚,V=5408.6Å3。该材料在室温下具有短波的近红外发光,其发射波长为856 nm,荧光量子产率可以达到12%;其结构具有较高的热稳定性,分解温度可以达到260oC。可以作为近红外荧光粉材料制备近红外LED,实现夜视近红外光照明。
Description
技术领域
本发明属于配位化学和纳米材料的交叉领域,主要涉及一种近红外发光的手性Cu6团簇材料。
背景技术
由几个乃至几百个金属原子及其外围保护配体组成的金属团簇材料,因精确的结构、优异的生物相容性以及光物理化学特性,在发光、催化、生物、纳米科学等领域具有广泛的应用前景。
近年来,Cu团簇因其合成成本低廉、光稳定性好、发光优异等优点,已经成为一类新型的纳米光学材料。在照明、光学探测、生物成像等领域具有广泛的应用价值。
通过近红外光实现夜间照明成像是一种具有广泛应用范围的技术,其对于夜间探测具有重要价值。近红外发光荧光粉材料是实现近红外荧光夜视成像的核心材料。目前报道的近红外荧光粉大多集中在无机材料领域,开发新型的近红外荧光粉对于拓展应用领域具有重要意义。
发明内容
本发明目的在于合成一种热稳定性高的近红外发光的手性Cu6团簇材料。
为此,本发明研发了一种近红外发光的手性Cu6团簇材料,其化学式为:C36H60Cu6N6S12,简写为:R/S-CS2,属于单斜晶系,空间群为手性空间群C2,S-CS2: α=90°,β=96.039°,γ=90°,R-CS2: α=90°,β=95.994°,γ=90°,
其中使用的手性配体为(S/R)-4-异丙基噻唑烷-2-硫酮(简写为:R/S-iptt),结构简式如下:
本发明手性Cu6团簇材料的制备方法通过如下步骤实现:
将碘化亚铜溶解在乙腈和N,N-二甲基甲酰胺混合溶剂中,加入配体(S/R)-4-异丙基噻唑烷-2-硫酮,搅拌反应,反应结束后,室温下避光挥发,得晶体,经过滤,洗涤,室温晾干即可。
所述Cu6团簇材料是由六个铜原子组成的内核以及外围六个有机配体共同组成的新材料(图1和图2所示);六个铜原子呈八面体排列,六个有机配体分别分布于八面体的六个面上,每个配体上的巯基硫原子同时与一个面上的两个铜原子配位,每个氮原子连接一个面上的另外一个铜原子(图3所示)。
本发明近红外发光的手性Cu6团簇材料,应用于近红外荧光照明,其性质具体描述如下:
所述材料具有较高的热稳定性,其分解温度可以达到260℃(图4所示)。在空气室温条件下具有较强的近红外荧光,其最佳发射波长位置为856nm(激发波长370nm)(图5所示);室温条件下荧光量子产率为12%。该材料在室温下可以被蓝光激发出较强的发光(图6所示),可以制备蓝光激发的近红外LED装置。将该材料的固体粉末与胶混合均匀涂抹在蓝光LED灯泡的表面,点亮LED灯,蓝光将该材料激发出近红外荧光,实现黑暗条件下的夜视照明(图7所示)
本发明有益效果:本发明Cu6团簇材料具有很宽的激发波段(300-660nm),可以被蓝光激发出强的近红外荧光;另外所述Cu6团簇材料具有较高的热稳定性(分解温度可以达到260℃)和发光效率(荧光量子产率为12%),在近红外LED夜视照明方面具有很好的应用前景。
附图说明
图1为本发明Cu6团簇材料的一对对映体结构示意图。
图2为本发明Cu6团簇材料的内核结构示意图。
图3为本发明Cu6团簇材料的配体配位模式示意图。
图4为本发明Cu6团簇材料热分析图。
图5为本发明Cu6团簇材料室温条件下荧光光谱图。
图6为本发明Cu6团簇材料在不同激发波长下的发射光谱图。
图7为本发明Cu6团簇材料作为近红外荧光材料制备的LED装置(a)、该装置点亮下的光谱(b)以及用该近红外LED装置发射的近红外光实现的夜视照明图片(c-d)。
具体实施方式
下面通过实例对本发明做进一步的说明:
实施例1:本发明Cu6团簇材料的合成
称取碘化亚铜(19mg,0.1mmol)溶于2mL乙腈和2.00mL N,N-二甲基甲酰胺混合溶剂中,然后加入(S/R)-4-异丙基噻唑烷-2-硫酮(16mg,0.1mmol),搅拌得到淡黄色清液。室温静置缓慢挥发4天即可得到黄色块状晶体,将晶体用乙腈洗涤并过滤收集,室温晾干用于其性质测试材料。
取实施例1制得的本发明Cu6团簇材料做进一步表征,其过程如下:
(1)晶体结构测定
配合物的X射线单晶衍射数据用大小合适的单晶样品在Rigaku XtaLAB Pro单晶衍射仪上测定。数据均用经石墨单色化的CuKα射线为衍射源通过ω扫描方式在300K温度下收集,并经过Lp因子校正和半经验吸收校正。结构解析是先通过SHELXS-97程序用直接法得到初结构,然后使用SHELXL-97程序用全矩阵最小二乘法精修。所有非氢原子均采用各向异性热参数法精修。所有的氢原子都采用各向同性热参数法精修。详细的晶体测定数据见表1。
表1本发明铜团簇材料的主要晶体学数据
表1主要晶体学数据
R1=∑||Fo|-|Fc||/∑|Fo|.wR2=[∑w(Fo 2-Fc 2)2/∑w(Fo 2)2]1/2
以上实施例仅用于说明本发明的内容,除此之外,本发明还有其它实施方式。但是,凡采用等同替换或等效变形方式形成的技术方案均落在本发明的保护范围内。
Claims (3)
2.如权利要求1所述的手性Cu6团簇材料,其特征在于:其内核是由六个铜原子组成,外围由六个有机配体保护;六个铜原子呈八面体排列,六个有机配体分别分布于八面体的六个面上,每个配体上的巯基硫原子同时与一个面上的两个铜原子配位,每个氮原子连接一个面上的另外一个铜原子。
3.如权利要求2所述的手性Cu6团簇材料在发光材料方面的应用,其特征在于:将该材料的固体粉末与胶混合,均匀涂抹在蓝光LED灯泡的表面,点亮LED灯,实现近红外光夜视照明。
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CN111548368A (zh) * | 2020-05-28 | 2020-08-18 | 安徽大学 | 一种具有高稳定性、近红外磷光的铜纳米团簇及其制备方法 |
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CN110467631A (zh) * | 2019-08-29 | 2019-11-19 | 郑州大学 | 一种具有聚集诱导发光和圆偏振发光的铜(i)炔簇 |
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