可逆SCSC转变中铜(Ⅱ)配合物的可视变色：结构对颜色的影响

doi:10.3866/PKU.DXHX202307050

Abstract

Abstract:

A comprehensive 8-hour chemical experiment was devised around the single crystal-to-single crystal (SCSC) transformation, an emerging method in solid-phase inorganic synthesis. By employing a direct additive process technology, the green complexes (H₃O)[K(15C5)₂][CuCl₄] (1) were synthesized in both powder and macro-single crystal forms. Upon temperature induction, complex 1 transitions to the red complex [K(15C5)₂][CuCl₃] (2), a shift attributed to the restricted dimerization of [CuCl₃]⁻ resulting from steric repulsion effects in the solid phase. Notably, complex 2 can revert back to complex 1 when exposed to hydrochloric steam through an SCSC transformation. This SCSC transformation between complexes 1 and 2 is vividly demonstrated on filter paper, showcasing dynamic color changes, either as texts or drawings. This rapid and visually engaging process is poised to spark students' curiosity. Furthermore, learners can bridge theory with practice, recognizing that the distinct colors of the two complexes arise from varying coordination numbers of copper (Ⅱ), grounded in the crystal field theory of inorganic chemistry. Characterization of the complexes was achieved using single crystal X-ray diffraction, powder X-ray diffraction, UV-visible spectroscopy, and Fourier transform infrared spectroscopy, confirming the differentiation of the complexes and the successful SCSC transformation. This aspect of the experiment allows students to hone their skills with the Cambridge crystal structure database and enhance their data analysis capabilities, fostering proficiency in operating large-scale instruments safely and accurately. With its streamlined design, modular teaching approach, and cost-effective reagents, this experiment is primed for integration into undergraduate curriculum for chemistry and related disciplines.

Key words: Single-crystal to single-crystal transformation, Copper (Ⅱ) complex, Steric repulsion effect, Crystal field theory, Comprehensive chemical experiment

Ji Qi, Jianan Zhu, Yanxu Zhang, Jiahao Yang, Chunting Zhang. Visible Color Change of Copper (Ⅱ) Complexes in Reversible SCSC Transformation: The Effect of Structure on Color[J].University Chemistry, 2024, 39(3): 43-57.

Figures/Tables 18

序号	用时		操作步骤
1	45 min		课前讲解
2	5 min	称量	称取0.85 g CuCl₂·2H₂O和0.37 g KCl置于同一个10 mL烧杯中
3	5 min	溶解	向烧杯中加入1.7 mL 10%盐酸，搅拌5 min至完全溶解
4	15 min	滴加反应	向混合液中滑入一枚磁子，于搅拌条件下向其中滴加2.0 mL15-冠-5，滴毕继续搅拌10 min
5	5 min	观察形貌	吸取反应液于载玻片上，用显微镜观察粉末样品的微观形貌
6	5 min	减压抽滤	减压抽滤反应液，滤饼为产品，滤液为培养晶体所需母液
7	5 min	晶体生长	将母液转移至烧杯中覆盖多孔滤纸，于通风橱中常温挥发，准备完毕后继续进行后续步骤
8	10 min	干燥	使用滤纸将产品压干，收集得到的绿色粉末
9	5 min	称量	称量压干后的产品，并称取其中0.30 g产品备用
10	20 min	观察现象	将产品转移至蒸发皿中，置于85 ℃恒温水浴锅上搅拌10 min，收集得到的红色粉末
11	5 min	称量	称量转变后的产品，并称取其中0.17 g产品备用
12	20 min	观察现象	将产品转移至滤纸上均匀铺展，置于盐酸气氛中反应10 min，收集得到的绿色粉末
13	5 min	称量	称量转变后的产品
14	10 min	样品准备	取一张空白滤纸，使用自加墨水笔蘸取抽滤瓶中的饱和溶液在滤纸上写字、画画
15	5 min	干燥	使用吹风机的冷风模式将滤纸吹干
16	10 min	观察现象	使用吹风机的热风模式吹扫滤纸10 min，观察滤纸上图样的颜色变化
17	10 min	观察现象	将滤纸置于盐酸气氛中保存10 min，观察滤纸上图样的颜色变化
18	10 min	课堂讨论	教师引导学生讨论滤纸上图样颜色变化的原因
19	5 min	观察形貌	观察绿色大晶体的生长情况及宏观形貌
20	5 min	减压抽滤	减压抽滤反应液，滤饼为配合物1大晶体
21	10 min	观察现象	将绿色大晶体转移至蒸发皿中，置于85 ℃恒温水浴锅上反应5 min，收集得到的红色大晶体
22	10 min	观察现象	将红色大晶体转移至滤纸上均匀铺展，置于盐酸气氛中反应5 min，收集得到的绿色大晶体
23	20 min	样品准备	学生分组进行对应仪器表征测试部分的样品准备
24	90 min	仪器表征	学生分组进行对应仪器表征测试
25	10 min	数据整理	填写原始实验数据记录册，由课代表统一拷贝仪器电脑上的测试文件，计算合成实验的产率
26	15 min	清洗仪器	产物回收，废液回收，仪器清洗整理
总时长	360 min

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试剂名称	纯度	试剂来源
氯化铜二水合物	AR	上海麦克林生化科技股份有限公司
氯化钾	99.5%	上海麦克林生化科技股份有限公司
去离子水	25 ℃电导率≤ 0.0548 μS∙cm⁻¹	实验室自制^a
盐酸	10%	由36%–38%盐酸(西陇科学股份有限公司)配制^b
15-冠醚-5	97%	上海麦克林生化科技股份有限公司
二甲基硅油	AR	上海麦克林生化科技股份有限公司
溴化钾	SP	上海麦克林生化科技股份有限公司
硫酸钡	SP	上海麦克林生化科技股份有限公司

仪器设备名称	仪器型号	制造商
电子天平	YP1002	上海佑科仪器仪表有限公司
电子分析天平	ME204/02	梅特勒-托利多仪器(上海)有限公司
数显恒温磁力搅拌器	85-2	常州越新仪器制造有限公司
循环水式多用真空泵	SHB-Ⅲ	北京浩海科仪科技有限公司
电热恒温水浴锅	DK-S22	上海精宏实验设备有限公司
双目生物显微镜	JS-500	北京京昊永成商贸有限公司
连续变倍体式显微镜	SG900	苏州神鹰光学有限公司
电热恒温鼓风干燥箱	DH-101-2BY	天津中环电炉股份有限公司
单晶X射线衍射仪	APEX Ⅱ	Bruker (德国)
粉末X射线衍射仪	XRD-6100	Shimadzu (日本)
紫外-可见分光光度计	UV-2600	Shimadzu (日本)
傅里叶变换红外光谱仪	ALPHA Ⅱ	Bruker (德国)

SCSC转变方向	转变前质量m₁/g	转变后质量m₂/g	质量差实验值(m₂ − m₁)/g	质量差理论值/g
配合物1→配合物2	0.30	0.28	−0.02	−0.02
配合物2→配合物1	0.17	0.18	0.01	0.01

晶胞参数	配合物1	配合物2	配合物1-re
晶系	三斜	单斜	三斜
a/Å ^a	13.05	9.10	13.10
b/Å	14.33	28.25	14.30
c/Å	17.23	11.82	17.27
α	90.54°	90°	90.81°
β	97.67°	103.43°	98.16°
γ	101.12°	90°	100.86°
V/Å³	3130	2954	3094

配合物	υ(O―H)/cm⁻¹	υ_as(CH₂)/cm⁻¹	υ_s(CH₂)/cm⁻¹	δ(O―H)/cm⁻¹	δ(CH₂)/cm⁻¹	υ_as(C―O―C)/cm⁻¹	υ_s(C―O―C)/cm⁻¹
1	3441 m, b	2903 s	2869 s	1633 w	1456 w, 1355 m	1118 vs, 1091 vs	941 s
2	–	2922 s	2865 s	–	1456 w, 1356 m	1121 vs, 1093 s	940 s
1-re	3444 m, b	2921 s	2868 s	1631 w	1455 w, 1357 m	1121 vs, 1092 s	941 s

Visible Color Change of Copper (Ⅱ) Complexes in Reversible SCSC Transformation: The Effect of Structure on Color

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试剂名称	价格	用量	成本
氯化铜二水合物	0.158元/g	0.85 g	0.13元
氯化钾	0.072元/g	0.37 g	0.03元
盐酸	0.050元/mL	4.0 mL ^b	0.20元
15-冠醚-5	6.590元/g	2.23 g	14.70元
二甲基硅油	0.228元/mL	1.0 mL	0.23元
溴化钾	3.196元/g	0.15 g	0.48元
硫酸钡	1.392元/g	1.00 g	1.39元
总计			17.16元

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