CN116041722B - 具有可见光催化c-c键偶联性能的铜簇-吩噁嗪基金属有机框架的制备方法及应用 - Google Patents
具有可见光催化c-c键偶联性能的铜簇-吩噁嗪基金属有机框架的制备方法及应用 Download PDFInfo
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- TZMSYXZUNZXBOL-UHFFFAOYSA-N 10H-phenoxazine Chemical compound C1=CC=C2NC3=CC=CC=C3OC2=C1 TZMSYXZUNZXBOL-UHFFFAOYSA-N 0.000 claims description 5
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- VMQMZMRVKUZKQL-UHFFFAOYSA-N Cu+ Chemical compound [Cu+] VMQMZMRVKUZKQL-UHFFFAOYSA-N 0.000 description 1
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
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- DBGUUPDUZXSAJF-UHFFFAOYSA-N [Cu+].[I+] Chemical compound [Cu+].[I+] DBGUUPDUZXSAJF-UHFFFAOYSA-N 0.000 description 1
- CLWRFNUKIFTVHQ-UHFFFAOYSA-N [N].C1=CC=NC=C1 Chemical group [N].C1=CC=NC=C1 CLWRFNUKIFTVHQ-UHFFFAOYSA-N 0.000 description 1
- 230000002159 abnormal effect Effects 0.000 description 1
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- 150000001336 alkenes Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
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- 230000000975 bioactive effect Effects 0.000 description 1
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- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
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- 229910001431 copper ion Inorganic materials 0.000 description 1
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 description 1
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- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 239000002638 heterogeneous catalyst Substances 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 125000002346 iodo group Chemical group I* 0.000 description 1
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- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
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Abstract
本发明属于光催化材料技术领域，一种具有可见光催化C‑C键偶联性能的铜簇‑吩噁嗪基金属有机框架的制备方法及应用，其中制备方法，是以3,7‑二吡啶‑10‑(4‑吡啶苯基)吩噁嗪TPPP作为有机配体、碘化亚铜作为金属盐，通过溶剂热法制得铜簇‑吩噁嗪基金属有机框架Cu2I2‑TPPP，其合成路线如下：TPPP+CuI→Cu2I2‑TPPP；本发明制备的目标材料Cu2I2‑TPPP，能够在其孔道内与底物发生弱相互作用，促进光激发条件下金属有机框架材料与底物之间的电子转移过程。同时其具有较宽的可见光吸收范围，良好的热稳定性；能够多次循环利用，利于回收，另外还具有制备简单，原料廉价等优点。
Description
技术领域
本发明涉及一种具有可见光催化C-C键偶联性能的铜簇-吩噁嗪基金属有机框架的制备方法及应用，属于光催化材料技术领域。
背景技术
C-C键的形成是化学合成中最基本的任务之一，也是有机化学的核心。在过去的50年里，过渡金属催化的交叉偶联反应改变了有机化合物的构造方式，通过过渡金属催化的碳-碳成键反应的重要性已被认可。
Sonogashira偶联反应是通过C-C键偶联合成二取代炔烃衍生物的最有效方法之一，广泛用于天然产物合成、生物活性药物和材料科学中的中间体制备。经典Sonogashira反应包括末端炔与卤代芳烃、烯烃的偶联。在常规条件下，Sonogashira偶联反应由钯(0)配合物和铜(I)卤化物共同催化，需要使用较高负载量的钯催化剂和更高负载量、甚至亚当量的铜催化剂；另外，钯催化剂成本高昂；这些因素限制了该反应的大规模工业应用。此外，日益增长的环境担忧也促使科学家开发对生态系统影响最小的新合成方法。近年来，以相对廉价且低毒性的过渡金属基催化剂取代昂贵、有毒的钯基催化体系，成为催化偶联的重要发展趋势，基于钴、镍、铜等金属的各种催化偶联反应体系得到开发。其中，铜盐及铜配合物具有较低的价格和相对低的毒性，可见光引发的铜氧化还原催化具有替代钯-铜催化体系、实现Sonogashira偶联等C-C键生成反应的潜力，受到广泛关注。
然而，光引发的铜氧化还原催化同样需要较高负载量的铜盐或铜配合物，在均相催化反应结束后，难以通过简单的分离除去，进而造成产物中较难避免的重金属残留。对于催化合成人用医药类化合物的质量控制而言，需严格限定有潜在毒害的过渡金属催化剂使用，且产物中金属残留须处于极低水平。这为光引发铜催化C-C键生成的进一步发展提出了挑战，也引发了将均相光催化体系进行非均相化的思路。然而，现有基于负载化一价铜离子和一价铜簇的非均相光催化体系，存在催化中心结构不明确，构效关系难以辨析，可见光吸收能力低等局限。金属有机框架(Metal-Organic Frameworks,MOFs)作为一类新型的晶态多孔材料，具有结构可设计、功能可调节的优点，其比表面积大、易于引入多种催化功能中心、且易于合成，因而是良好的非均相催化剂的设计平台；更重要的是，MOFs结构的长程有序性，为深入理解光催化构效关系并进行迭代设计提供了便利。MOFs在开发催化系统以促进交叉耦合反应方面具有很大的灵活性。基于MOFs平台开发的非均相过渡金属催化偶联反应体系，已经初步应用于如Suzuki-Miyaura,Mizoroki-Heck，Stille，Ullmann等著名人名反应。我们注意到，将一价铜簇和具有可见光吸收能力的染料同时引入MOFs，构建新型的、具有底物活化和光氧化还原双功能的非均相光催化平台，目前尚处于研究空白。
吩噁嗪及其衍生物是一种具有非平面蝴蝶构象的富电子光敏基元。具有特殊的构象以及光物理性质，相比于其他有机光敏剂有着较好的催化能力。吩噁嗪类衍生物有着较高的激发态还原电位、较高的空穴迁移率和较强的光稳定性，并且易于修饰从而连接具有配位能力或扩大其共轭体系的官能团。
本发明专利将铜-卤簇结构与吩噁嗪基配体TPPP共同构筑到金属有机框架材料中，得到了具有三维结构的铜(Ⅰ)碘簇的金属有机框架材料。利用吩噁嗪基配体的还原型光敏中心和铜催化中心的协同作用，通过构建非均相的光催化反应体系，在温和反应条件下根据催化反应氛围的调控可切换催化偶联的不同反应模式和选择性，分别在氮气氛围下实现末端炔烃与卤代烷基的异型C-C偶联反应、以及在氧化氛围下实现末端炔烃的C-C自耦联反应，具有鲜明的创新性和应用便利性。
发明内容
为了克服现有技术中存在的不足，本发明目的是提供一种具有可见光催化C-C键偶联性能的铜簇-吩噁嗪基金属有机框架的制备方法及应用。采用这种制备方法得到的铜簇-吩噁嗪基金属有机框架目标材料能够在其孔道内与底物发生弱相互作用，促进光激发条件下金属有机框架材料与底物之间的电子转移过程。同时其具有较宽的可见光吸收范围，良好的热稳定性；能够多次循环利用，利于回收，另外还具有制备简单，原料廉价等优点。
为了实现上述发明目的，解决已有技术中所存在的问题，本发明采取的技术方案是：一种具有可见光催化C-C键偶联性能的铜簇-吩噁嗪基金属有机框架的制备方法，是以3,7-二吡啶-10-(4-吡啶苯基)吩噁嗪TPPP作为有机配体、碘化亚铜作为金属盐，通过溶剂热法制得铜簇-吩噁嗪基金属有机框架Cu2I2-TPPP，其合成路线如下：
TPPP+CuI→Cu2I2-TPPP；
所述有机配体TPPP，具有如下(A)分子结构式，
所述有机配体TPPP的制备过程已被本申请人于2021年12月24日(专利名称：具有可见光催化还原C-F键性能的吩噁嗪基金属有机框架的制备方法及应用，专利号：202111609429.7)所公开，属于公开技术。
所述Cu2I2金属-配体簇，具有如下(B)晶体结构，
所述铜簇-吩噁嗪基金属有机框架Cu2I2-TPPP的制备方法，包括以下步骤：
步骤1、称取有机配体TPPP与碘化亚铜按照1：1.5～2.5的摩尔比加入到盛有2～5mL N,N-二甲基乙酰胺的耐热玻璃瓶中，超声分散均匀；
步骤2、将分散均匀的原料加入到带有聚四氟内衬的水热反应釜中并加以密封，随后放入带有控温程序的烘箱中，升温到110～140℃，保持恒温反应70～80h；
步骤3、反应结束降至室温后，移去上清液，加入乙醇洗涤，离心，反复操作2～3次，收集底部晶体，得到橙色块状晶体，即目标材料铜簇-吩噁嗪基金属有机框架Cu2I2-TPPP。
所述方法制备的铜簇-吩噁嗪基金属有机框架Cu2I2-TPPP在光催化C-C键反应中的应用。
本发明有益效果是：一种具有可见光催化C-C键偶联性能的铜簇-吩噁嗪基金属有机框架的制备方法及应用，其中制备方法，是以3,7-二吡啶-10-(4-吡啶苯基)吩噁嗪TPPP作为有机配体、碘化亚铜作为金属盐，通过溶剂热法制得铜簇-吩噁嗪基金属有机框架Cu2I2-TPPP，其合成路线如下：TPPP+CuI→Cu2I2-TPPP；利用本发明方法制备的铜簇-吩噁嗪基金属有机框架Cu2I2-TPPP的晶体结构属于四方晶系，P42/nmc空间群，其非对称结构单元由3/2个晶体学独立的Cu原子、3/2个晶体学独立的Cu原子和1个吩噁嗪基配体(TPPP)组成。结构中所有的Cu原子均为扭曲的四面体构型的四配位模式。铜与两个碘原子和两个来自不同吩噁嗪基配体(TPPP)的吡啶氮原子进行配位。Cu…Cu间的距离约为N-Cu-N的夹角约为102.9°，I-Cu-I的夹角约为122.1°。此晶体结构为三维穿插结构，穿插结构中两吩噁嗪基配体(TPPP)母核部分的面面距离最小约/>有明显的π···π堆积作用。在晶体沿c轴方向上形成的四边形孔道中，相对I原子的距离为/>在将Cu2I2簇构筑到结构中后，Cu2I2-TPPP中的吩噁嗪基配体(TPPP)也保持了高密度的堆积。在385nm波长的LED照射下能够催化Sonogashira偶联反应，通过炔烃与芳基卤代物反应得到C-C偶联产物。本发明制备的目标材料Cu2I2-TPPP，产率高且化学性质稳定，制备工艺简单，成本低，易于大规模制备。
附图说明
图1是实施例1目标材料Cu2I2-TPPP的晶体结构示意图。
图2是实施例2目标材料Cu2I2-TPPP的循环伏安图。
图3是实施例2目标材料Cu2I2-TPPP和配体TPPP的EIS电化学阻抗图。
图4是实施例2目标材料Cu2I2-TPPP和配体TPPP的光电流测试谱图。
图5是实施例3目标材料Cu2I2-TPPP的紫外可见吸收谱图。
图6是实施例4目标材料Cu2I2-TPPP的荧光发射谱图。
图7是实施例6目标材料Cu2I2-TPPP的催化循环产率示意图。
图8是实施例6目标材料Cu2I2-TPPP的PXRD图。
具体实施方式
下面结合实施例对本发明作进一步说明。
实施例1
称取TPPP(2.5mg,5μmol)与碘化亚铜(2.0mg,10μmol)加入到盛有3mLN,N-二甲基乙酰胺的耐热玻璃瓶中，逐瓶称量30瓶，原料均匀分散后，加入到带有聚四氟内衬的水热反应釜中并加以密封，随后放入带有控温程序的烘箱中，升温到120℃保持恒温反应72h，降至室温后，移去上清液，加入乙醇洗涤，离心，反复操作3次，收集底部晶体，得到橙色块状晶体，即目标材料铜簇-吩噁嗪基金属有机框架Cu2I2-TPPP 58mg，产率43％，晶体结构如图1所示。
实施例2
称取2mg的Cu2I2-TPPP加入到0.5mL的乙醇中制成悬浮液，然后分别加入0.06mL的Nafion并通过超声混合，取0.2mL悬浮液涂敷于FTO玻璃表面，涂敷面积为1cm2，烘干，然后将FTO玻璃夹在电极夹上，作为工作电极。光电流测试在CHI 660E电化学工作站进行，采用三电极体系，Ag/AgCl电极作为参比电极，铂片电极作为对电极，0.10M的四丁基六氟磷酸铵的乙腈溶液作为电解液，Cu2I2-TPPP的循环伏安图，如图2所示，Cu2I2-TPPP和配体TPPP的EIS电化学阻抗图，如图3所示。光电流测试在1atm的氮气条件下测试，温度为室温，光源为50W的385nm波长的LED光源。Cu2I2-TPPP和配体TPPP的光电流测试谱图，如图4所示。光电流以及电化学阻抗的测试均表明，相较于配体TPPP，Cu2I2-TPPP的电阻更小，光响应更强，受光激发后，电荷分离的效率更高，有着更高的光催化活性。
实施例3
称取5mg的Cu2I2-TPPP加入到玛瑙研钵中并将其研磨成粉末，再将其置于石英玻璃片的凹槽中心，用另一块石英玻璃片覆盖住凹槽，细微调节两片石英玻璃片的位置，使粉末在凹槽中尽量分布均匀没有空隙。Cu2I2-TPPP的紫外可见吸收谱图，如图5所示，反映了Cu2I2-TPPP的吸光性质。相较于吩噁嗪基配体TPPP，Cu2I2-TPPP有着更宽的吸收范围，几乎涵盖整个可见光区，其中400nm～500nm归属于吩噁嗪基配体TPPP的吸收，而峰值在500nm，吸收范围在500nm～800nm的较弱吸收带归属为金属到配体的电荷转移(MLCT)吸收峰。Cu2I2-TPPP吸收峰的宽化有利于对光的吸收，从而提高可见光催化的催化效率。
实施例4
称取2mg的Cu2I2-TPPP加入到10mL的乙腈中制成均匀且较透光的悬浮液，转移到带塞荧光池中，鼓入氩气15min，确保悬浊液在无氧条件下。在FLS1000仪器上进行荧光测试，选取激发波长385nm，得到Cu2I2-TPPP的荧光发射图谱，如图6所示。相较于吩噁嗪基配体TPPP的荧光发射峰可以得出，590nm附近的荧光发射峰主要归属于框架内吩噁嗪基配体TPPP的本征荧光发射峰。450nm处荧光发射峰的降低说明可能受到金属簇Cu2I2的影响，框架内发生了卤素到配体的电荷转移(XLCT)过程。
实施例5
向干燥的光反应管中加入Cu2I2-TPPP(0.01mmol，5mol％，7.80mg)，K2CO3(2eq,0.4mmol,55.3mg)用翻口塞密封,对反应体系进行“抽真空/通氮气”处理三次，除去固体体系中的氧气。用长针头向反应管中加入干燥脱气后的乙腈(3mL)，苯乙炔(1eq,0.2mmol,22μL)，芳基卤代物(1eq,0.2mmol)；然后用Parafilm封口膜密封反应管穿刺处，于385nm LED光源照射下室温搅拌24h。通过有机滤膜分离催化剂，滤液旋干，粗产物通过薄层色谱法进行分离。Cu2I2-TPPP催化C-C键偶联的底物拓展，如表1所示。
表1
实施例6
向干燥的光反应管中加入Cu2I2-TPPP(0.01mmol，5mol％，7.80mg)，K2CO3(2eq,0.4mmol,55.3mg)用翻口塞密封,对反应体系进行“抽真空/通氮气”处理三次，除去固体体系中的氧气。用长针头向反应管中加入干燥脱气后的乙腈(3mL)，苯乙炔(1eq,0.2mmol,22μL)，(1-溴乙基)苯(1eq,0.2mmol，27μL)；然后用Parafilm封口膜密封反应管穿刺处，于385nm LED光源照射下室温搅拌24h。催化反应结束后，离心过滤得到反应后的Cu2I2-TPPP粉末，进行下一次反应循环，催化循环产率示意图，如图7所示。Cu2I2-TPPP重复利用三次反应后，经X射线粉末衍射测试(PXRD)，其结构大致保持，如图8所示。
实施例7
向洁净干燥的石英光反应管中加入Cu2I2-TPPP(0.01mmol，5mol％，7.80mg)，K2CO3(2eq,0.4mmol,55.3mg)用翻口塞密封,对反应体系进行“抽真空/通氮气”处理三次，除去固体体系中的氧气。用长针头向反应管中加入干燥脱气后的乙腈(3mL)，芳基乙炔(1eq,0.2mmol)。反应开始后在橡胶塞上方插入细针头，使空气能够缓慢进入到体系中，在385nmLED光源照射下室温搅拌24h。反应结束后，通过离心分离催化剂，有机相过有机滤膜后收集并旋干，粗产物通过硅胶柱色谱分离。金属有机框架Cu2I2-TPPP作为光催化剂催化芳基乙炔C-H脱氢偶联反应，实现末端炔烃的脱氢自偶联。Cu2I2-TPPP催化C-C键自偶联的底物拓展，如表2所示。
表2
铜簇-吩噁嗪基金属有机框架Cu2I2-TPPP对Sonogashira偶联反应展现出良好的底物范围，适用于芳基卤代物、苄基卤代物等类型的自由基前体，以中等至良好产率得到具有重要用途的二取代乙炔砌块，该非均相催化光催化体系在精细化工医药和中间体合成领域具有良好的应用潜质。
Claims (2)
1.一种具有可见光催化C-C键偶联性能的铜簇-吩噁嗪基金属有机框架的制备方法，其特征在于：是以3,7-二吡啶-10-(4-吡啶苯基)吩噁嗪TPPP作为有机配体、碘化亚铜作为金属盐，通过溶剂热法制得铜簇-吩噁嗪基金属有机框架Cu2I2-TPPP，其合成路线如下：
TPPP+CuI→Cu2I2-TPPP；
所述有机配体TPPP，具有如下(A)分子结构式，
所述Cu2I2金属-配体簇，具有如下(B)晶体结构，
所述铜簇-吩噁嗪基金属有机框架Cu2I2-TPPP的制备方法，包括以下步骤：
步骤1、称取有机配体TPPP与碘化亚铜按照1：1.5～2.5的摩尔比加入到盛有2～5mL N,N-二甲基乙酰胺的耐热玻璃瓶中，超声分散均匀；
步骤2、将分散均匀的原料加入到带有聚四氟内衬的水热反应釜中并加以密封，随后放入带有控温程序的烘箱中，升温到110～140℃，保持恒温反应70～80h；
步骤3、反应结束降至室温后，移去上清液，加入乙醇洗涤，离心，反复操作2～3次，收集底部晶体，得到橙色块状晶体，即目标材料铜簇-吩噁嗪基金属有机框架Cu2I2-TPPP。
2.根据权利要求1所述方法制备的铜簇-吩噁嗪基金属有机框架Cu2I2-TPPP在光催化C-C键反应中的应用。
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