CN111517983B - 一种以光致变色材料螺吡喃为前驱体的化合物及其制备方法与应用 - Google Patents
一种以光致变色材料螺吡喃为前驱体的化合物及其制备方法与应用 Download PDFInfo
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Abstract
本发明属于光致变色材料领域,公开了一种以光致变色材料螺吡喃为前驱体的化合物及其制备方法,独创性地通过水热合成法,以N‑羟乙基‑3,3‑二甲基‑6‑硝基吲哚啉螺吡喃为配体,合成了金属有机框架配合物C16H12CuN4O6,通过表征发现,螺吡喃配体与乙二胺发生了原位反应,形成了席夫碱配体,金属Cu与席夫碱配体配位形成四配位的配合物C16H12CuN4O6。本发明还公开了所述以光致变色材料螺吡喃为前驱体的化合物在光催化降解染料中的应用。
Description
技术领域
本发明属于光致变色材料领域,具体涉及一种以光致变色材料螺吡喃为前驱体的化合物及其制备方法与应用。
背景技术
光致变色是一种化学物理现象。其包含无机、有机、生物及聚合物等光诱导的化学和物理反应。对光致变色材料来说,光致变色过程是分子吸收不同波长光子后,通过电子跃迁来实现的,直接实现信息存储,不需要经过光和热的转化,因此,被称光子型存储。在受到一定强度和波长的光照射下,通过特定的光化学反应,一个化合物A可以转化为产物B。由于化合物结构、电子组态的改变,化合物的吸收光谱亦发生明显的变化,即颜色发生变化。反之在另一不同强度和波长光的照射下,化合物B又能恢复到A的现象,这就是光致变色现象。光致变色化合物就是一类能在光的作用下发生可逆颜色变化的化合物。通常,大多数光致变色体都属予单分子反应。
光致变色材料从材料可分为无机光致变色材料、有机光致变色材料两大类。其中,有机光致变色材料不仅可以通过改变分子结构来调变其光学和热学性能,而且有机光致变色材料具有良好的灵敏性、清晰度、柔顺性,从而成为了光致变色材料的研究热点。
目前,对有机光致变色材料的研究大都集中在螺吡喃、偶氮类、二芳基乙烯、俘精酸酐类化合物等领域。其中,偶氮苯及其衍生物是一类人们研究比较广泛的顺反异构型化合物。偶氮苯类化合物能够进行顺反异构化,属于有机光致变色体系。在紫外光照下,反式的偶氮苯转变为顺式,因此,紫外-可见吸收光谱上的最大吸收波长也随之改变。并且,由于顺式偶氮苯热稳定性较差,在可见光或热的作用下,会发生可逆反应回到反式结构。但是,这类光致变色化合物不仅热稳定性差,而且光致变色前后的吸收光谱变化小,因此在一定程度上,偶氮苯类化合物的实际应用受到限制。
为了避免热稳定性较差的问题,研究目光又集中于螺吡喃类和螺噁嗪类化合物。中心螺碳原子分别连接了分子中的苯并吡喃环和吲哚啉环,所以两个环相互正交,不存在共轭。在紫外光(<410nm)照射下,分子中螺环处的碳-氧键发生断裂,电子排布和分子构象发生改变。螺碳原子从sp3结构转变为sp2结构,两个环变为平面型结构,分子的紫外-可见吸收光谱在500~600nm处出现一个强的吸收峰,此处变为有色的开环态-部花菁。撤去光照后,部花菁分子又经可逆反应转变回无色的闭环态螺吡喃。
因此,开发一种四配位结构的以光致变色材料螺吡喃为前驱体的金属有机框架化合物成为了本领域技术人员亟需解决的问题。
发明内容
有鉴于此,本发明的目的是针对现有技术中存在的问题,提供一种以光致变色材料螺吡喃为前驱体的化合物。
为了实现上述目的,本发明采用如下技术方案:
一种以光致变色材料螺吡喃为前驱体的化合物,所述化合物为金属有机框架配合物C16H12CuN4O6,结构如式1,其中,金属Cu与席夫碱配体配位形成四配位结构,
本发明的第二个目的在于,提供所述以光致变色材料螺吡喃为前驱体的化合物的制备方法。
为了实现上述目的,本发明提供如下技术方案:
所述的以光致变色材料螺吡喃为前驱体的化合物的制备方法,将Cu(NO3)2、N-羟乙基-3,3-二甲基-6-硝基吲哚啉螺吡喃、乙二胺混匀于N,N’-二甲基甲酰胺DMF和正丙醇中,80℃下恒温放置72h,得到以光致变色材料螺吡喃为前驱体的化合物C16H12CuN4O6。
值得说明的是,本发明通过水热合成法,以N-羟乙基-3,3-二甲基-6-硝基吲哚啉螺吡喃为配体,合成了金属有机框架配合物C16H12CuN4O6。与预期的过渡金属阳离子直接与螺吡喃分子率先进行配位不同,表征发现,本发明反应体系中的螺吡喃配体首先与乙二胺发生了原位反应,形成席夫碱配体,然后金属Cu再与席夫碱配体配位形成四配位的配合物C16H12CuN4O6。
进一步地,所述Cu(NO3)2与N-羟乙基-3,3-二甲基-6-硝基吲哚啉螺吡喃的摩尔比为3:1,所述乙二胺、N,N’-二甲基甲酰胺DMF和正丙醇的体积比为1:10:30,且反应体系中所述N-羟乙基-3,3-二甲基-6-硝基吲哚啉螺吡喃的浓度为0.025±0.002mol/L。
值得说明的是,本发明将Cu(NO3)2、N-羟乙基-3,3-二甲基-6-硝基吲哚啉螺吡喃、乙二胺无差别混匀于N,N’-二甲基甲酰胺DMF和正丙醇中,与现有技术中认为的过渡金属阳离子与螺吡喃配体发生配位反应不同,本发明发现螺吡喃配体可以与乙二胺发生原位反应形成席夫碱配体后,再与金属Cu形成四配位化合物。该化合物在紫外光(<410nm)照射下,分子中螺环处的碳-氧键发生断裂,电子排布和分子构象发生改变,螺碳原子从sp3结构转变为sp2结构,两个环变为平面型结构,分子的紫外-可见吸收光谱在500~600nm处出现强吸收峰,成为有色的开环态-部花菁,光照消失后,部花菁分子又经可逆反应转变回无色的闭环态螺吡喃,恢复初始状态。
本发明的第三个目的在于提供所述以光致变色材料螺吡喃为前驱体的化合物的应用。
为了实现上述目的,本发明提供如下技术方案:
所述以光致变色材料螺吡喃为前驱体的化合物在光催化降解染料中的应用。
进一步地,所述光催化降解的反应条件为将以光致变色材料螺吡喃为前驱体的化合物和染料的混合溶液在避光条件下混匀,在紫外光照下进行光催化反应。
本发明与现有技术相比,具有以下优点和有益效果:
1、本发明独创性地合成了一种金属Cu与席夫碱配体配位形成四配位的光致变色配合物C16H12CuN4O6,该化合物打破了前人认为的螺吡喃类配体会直接与过渡金属阳离子发生配位反应的认知,在螺吡喃类配体、乙二胺和过渡金属阳离子共混的情况下,首先由螺吡喃配体与乙二胺发生原位反应形成席夫碱配体,然后再与金属Cu形成四配位化合物。
2、本发明的以光致变色材料螺吡喃为前驱体的化合物,可以在紫外光照射下实现染料的光催化降解。
3、本发明提供的一步水热合成法制备方法简单、原料易得、合成步骤少、合成条件温和,产率较高,具有产业化应用的潜力。
附图说明
为了更清楚地说明本发明实施例或现有技术中的技术方案,下面将对实施例或现有技术描述中所需要使用的附图作简单地介绍,显而易见地,下面描述中的附图仅仅是本发明的实施例,对于本领域普通技术人员来讲,在不付出创造性劳动的前提下,还可以根据提供的附图获得其他的附图
图1为本发明以光致变色材料螺吡喃为前驱体的化合物粉末X-射线衍射图:理论和实验PRRD的对比图。
图2为本发明以光致变色材料螺吡喃为前驱体的化合物中Cu的配位环境示意图。
图3为本发明以光致变色材料螺吡喃为前驱体的化合物氢键作用形成的1D链结构示意图。
图4为本发明以光致变色材料螺吡喃为前驱体的化合物氢键作用形成的2D层状结构示意图。
图5为本发明以光致变色材料螺吡喃为前驱体的化合物氢键作用形成的3D骨架结构示意图。
图6为本发明以光致变色材料螺吡喃为前驱体的化合物的IR光谱图。
图7为本发明以光致变色材料螺吡喃为前驱体的化合物对亚甲基蓝的光催化降解的紫外吸收光谱图。
图8为本发明以光致变色材料螺吡喃为前驱体的化合物对盐酸副玫瑰苯胺的光催化降解的紫外吸收光谱图。
图9为本发明以光致变色材料螺吡喃为前驱体的化合物对亚甲基蓝和盐酸副玫瑰苯胺的光催化降解率对比图。
具体实施方式
下面将对本发明实施例中的技术方案进行清楚、完整地描述,显然,所描述的实施例仅仅是本发明一部分实施例,而不是全部的实施例。基于本发明中的实施例,本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例,都属于本发明保护的范围。
为更好地理解本发明,下面通过以下实施例对本发明作进一步具体的阐述,但不可理解为对本发明的限定,对于本领域的技术人员根据上述发明内容所作的一些非本质的改进与调整,也视为落在本发明的保护范围内。
实施例1
一种以光致变色材料螺吡喃为前驱体的化合物及其制备方法,将0.3mmol Cu(NO3)2、0.1mmolN-羟乙基-3,3-二甲基-6-硝基吲哚啉螺吡喃、0.1mL乙二胺、1mLN,N’-二甲基甲酰胺DMF和3mL正丙醇加入小玻璃瓶中,80℃条件下反应72h,得到棕黄色晶体,即为化合物C16H12CuN4O6。
实施例2
一种以光致变色材料螺吡喃为前驱体的化合物在光催化降解染料中的应用,包括以下步骤:
步骤I、盐酸副玫瑰苯胺溶液的配制:
称取3mg盐酸副玫瑰苯胺(Pra)于烧杯中,溶解,转移至500mL容量瓶,定容至刻度线,配制成浓度为6mg/L的盐酸副玫瑰苯胺水溶液,待用;
步骤II、化合物C16H12CuN4O6的光催化测定:
称取20mg化合物于烧杯中,加入40mL盐酸副玫瑰苯胺水溶液,在黑暗中用磁力搅拌器搅拌30min,直至达到吸附-去吸附过程平衡。在光照下进行光催化反应。每隔30min静置后移取上层清液4mL于试管中,用所得澄清溶液进行紫外光谱检测,紫外检测波长范围是350到650nm。
实施例3
一种以光致变色材料螺吡喃为前驱体的化合物在光催化降解染料中的应用,包括以下步骤:
步骤I、亚甲基蓝溶液的配制:
称取3mg亚甲基蓝(MB)于烧杯中,溶解,然后转移至500mL容量瓶中,定容至刻度线,配制成浓度为6mg/L的亚甲基蓝水溶液,待用;
步骤II、化合物C16H12CuN4O6的光催化测定:
称取20mg化合物于烧杯中,加入40mL亚甲基蓝水溶液,在黑暗中用磁力搅拌器搅拌30min,直至达到吸附-去吸附过程平衡。在光照下进行光催化反应。每隔30min静置后移取上层清液4mL于试管中,用所得澄清溶液进行紫外光谱检测,紫外检测波长范围是500到800nm。
为了进一步证明本发明的有益效果以更好地理解本发明,下面通过以下测定试验进一步阐明本发明所述以光致变色材料螺吡喃为前驱体的化合物的具有的性质及应用性能,但不可理解为对本发明的限定,对于本领域的技术人员根据上述发明内容所作的其他测定实验得到的产品性质及根据上述性质进行的应用,也视为落在本发明的保护范围内。
实验例1
目标产物纯度表征:
采用具有D/teX超级衍射仪和以Cu Kα放射源的Ultima IV在30kV和20mA的条件下检测实施例1的目标产物化合物C16H12CuN4O6的X-射线粉末衍射(PXRD)数据。如图1所示,化合物的X-射线粉末衍射结果与晶胞模拟结果中的衍射峰在关键的位置均是相匹配的,说明化合物是单一相的纯度。衍射峰强度的不同可能是由于在实验PXRD模式收集数据过程中,粉末择优取向的变化。
实验例2
晶体结构表征:
在室温下,通过显微镜观察选取合适大小的实施例1的目标产物晶体,在室温下进行X-射线衍射实验。晶体的X-射线衍射数据在Oxford Diffraction Gemini R Ultra衍射仪上收集,用经石墨单色器单色化的Cu-Kα射线 在296K温度下以φ-ω方式收集衍射数据。部分结构的衍射数据使用SADABS程序进行吸收校正。晶体结构由直接法结合差值Fourier合解。所有非氢原子坐标及各向异性参数进行全矩阵最小二乘法修正,C–H原子的位置按理论模式计算从而确定,O–H原子首先根据差值Fourier找到,然后,其氢原子坐标及各向同性参数进行全矩阵最小二乘法修正,并参与最终结构精修。其中,化合物C16H12CuN4O6的晶体学参数见表1,化合物C16H12CuN4O6的主要键长和键角列于表2和表3中,化合物含有弱的氢键作用列于表4。
表1化合物C16H12CuN4O6的晶体学数据和结构参数
表3化合物C16H12CuN4O6主要的键角(°)
表4化合物C16H12CuN4O6中的氢键作用
通过上述表1~表4表征信息可知,化合物C16H12CuN4O6结晶在三斜空间群P-1中,且结构中包含一个Cu(Ⅱ)离子,一个由一分子的乙二胺和两分子的N-羟乙基-3,3-二甲基-6-硝基吲哚啉螺吡喃配体自组装形成的席夫碱配体,Cu呈现出不饱和的四配位结构,分别与一个席夫碱配体中的两个N原子,两个羟基O原子配位(图2)。Cu1-O1和Cu1-O2的键长分别为1.9188(19)和Cu1-N1和Cu1-N2的键长分别为1.944(2)和
单核Cu结构通过氢键作用C(16)–H(16)…O(5)形成一维链,进而通过氢键作用C(8)–H(8)…O(3)形成的一维带状链;1D链通过氢键作用C(3)–H(3)…·O(6)和C(8)–H(8)…O(3)形成二维超分子层结构,并进一步通过另一种氢键作用C(16)–H(16)…O(5)形成三维超分子骨架(图3~5)。
实验例3
化合物的红外光谱分析:
如图6所示,在实施例1的目标产物化合物C16H12CuN4O6中,789.01,901.84cm-1处的峰分别为苯环上邻位,对位取代的特征吸收峰,1047.27,1102.33cm-1处的峰应该是苯环上νas(C-H)的伸缩振动特征吸收峰,1461.62cm-1处的峰一般为νas(-CH2)的特征吸收峰,1552.06,1497.01cm-1处的峰应该是νas(Ar-NO2)的特征吸收峰,2924.33cm-1处的峰应该是νas(-Ph)的特征吸收峰,3434.57,3309.46cm-1处的峰应该是νas(C-N)的特征吸收峰,1600.07,1643.97cm-1处的峰应该为νas(C-O)的特征吸收峰。
实验例4
利用TU-1901双光束紫外可见分光光度计对实施例2、实施例3光催化降解应用中的化合物C16H12CuN4O6的光降解性能进行表征,图7~8是化合物C16H12CuN4O6对亚甲基蓝和盐酸副玫瑰苯胺的光催化降解紫外吸收光谱图,从图中可以明显看出化合物C16H12CuN4O6对亚甲基蓝和盐酸副玫瑰苯胺都有催化降解作用,在化合物C16H12CuN4O6的存在下,亚甲基蓝溶液和盐酸副玫瑰苯胺溶液的吸收峰都是随着时间的增加而减弱,但是它们的光催化效率是不同的。如图9所示,盐酸副玫瑰苯胺溶液在3小时光照后的降解率达到36.92%,而亚甲基蓝的降解率只有20.93%。化合物C16H12CuN4O6对于盐酸副玫瑰苯胺溶液的催化效率要大于亚甲基蓝溶液。
对所公开的实施例的上述说明,使本领域专业技术人员能够实现或使用本发明。对这些实施例的多种修改对本领域的专业技术人员来说将是显而易见的,本文中所定义的一般原理可以在不脱离本发明的精神或范围的情况下,在其它实施例中实现。因此,本发明将不会被限制于本文所示的这些实施例,而是要符合与本文所公开的原理和新颖特点相一致的最宽的范围。
Claims (2)
1.一种以光致变色材料螺吡喃为前驱体的化合物的制备方法,其特征在于,将Cu(NO3)2、N-羟乙基-3,3-二甲基-6-硝基吲哚啉螺吡喃、乙二胺混匀于N,N’-二甲基甲酰胺DMF和正丙醇中,80℃下恒温放置72h,得到以光致变色材料螺吡喃为前驱体的化合物C16H12CuN4O6,结构如式1,其中,金属Cu与席夫碱配体配位形成四配位结构,
2.根据权利要求1所述的一种以光致变色材料螺吡喃为前驱体的化合物的制备方法,其特征在于,所述Cu(NO3)2与N-羟乙基-3,3-二甲基-6-硝基吲哚啉螺吡喃的摩尔比为3:1,所述乙二胺、N,N’-二甲基甲酰胺DMF和正丙醇的体积比为1:10:30,且反应体系中所述N-羟乙基-3,3-二甲基-6-硝基吲哚啉螺吡喃的浓度为0.025±0.002mol/L。
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