CN109232616B - (–)-2-(4′-吡啶基)-4,5-蒎烯-吡啶手性银配合物及其制备方法 - Google Patents
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Abstract
本发明公开了一种(–)‑2‑(4′‑吡啶基)‑4,5‑蒎烯‑吡啶手性银配合物，配合物的分子式为[Ag(L)ClO4]∞，本发明将手性单齿含N有机配体L:[(–)‑2‑(4′‑吡啶基)‑4,5‑蒎烯‑吡啶]与AgClO4反应，得到的(–)‑2‑(4′‑吡啶基)‑4,5‑蒎烯‑吡啶手性银配合物的制备方法，工艺简单，常温常压反应，安全性好且成本低，后处理容易且产率高达86%；该配合物不但具有手性光学活性还具有吸收紫外光，产生可见光发射的能力，是同时具有手性光学活性和光转换能力的双功能材料，有望作为新型发光材料在圆偏振发光、荧光免疫分析、非线性光学材料以及光转换分子器件等方面有广阔的商业化应用前景。
Description
技术领域
本发明属于无机-有机杂化手性功能材料及其制备与应用技术领域，特别涉及一种具有可见光发光性能的手性银配合物及其制备方法。
背景技术
手性是物质的基本属性，在生物学、药物化学和材料科学中发挥重要的作用。手性结构的设计和合成长期以来一直是有趣的课题，吸引了许多研究领域科研工作者的广泛关注，不仅仅是因为它们具有与生物学相关的重要结构，同时也由于手性材料在非线性光学、不对称催化、对映体选择性吸附与分离等方面具有广阔的商业化应用前景。
在过渡金属配合物中，d10电子构型的银配合物具有独特的发光性能，是一类重要的分子基发光材料，成为配位化学和材料科学领域热门的研究课题。尤其是在发光的银配合物中引入手性，还可能赋予这类发光材料一些与手性相关的且有趣的物理性能如：手性圆偏振发光、手性荧光探针、手性感应等，是潜在的多功能材料。这类材料的设计和制备更是合成化学家和材料科学家们极为感兴趣的又具有挑战性的研究课题。
发明内容
本发明的目的是提供一种(–)-2-(4′-吡啶基)-4,5-蒎烯-吡啶手性银配合物发光材料及制备方法，该制备方法工艺简单，常温反应，后处理容易且产率高。
为实现上述目的，本发明采用以下技术方案：
一种(–)-2-(4′-吡啶基)-4,5-蒎烯-吡啶手性银配合物，所述(–)-2-(4′-吡啶基)-4,5-蒎烯-吡啶手性银配合物的分子式为[Ag(L)ClO4] ∞，其中L为手性单齿含N有机配体：(–)-2-(4′-吡啶基)-4,5-蒎烯-吡啶，结构式为
。
(–)-2-(4′-吡啶基)-4,5-蒎烯-吡啶手性银配合物的制备方法，步骤如下：
（1）将溶有高氯酸银AgClO4的甲醇溶液放入试管中作为底层，其中高氯酸银的浓度为0.01~0.02 mol/L；
（2）在底层上加入甲醇和二氯甲烷的混合溶液6~8 mL作为中间缓冲层；
（3）将溶有手性单齿含N有机配体L：(–)-2-(4′-吡啶基)-4,5-蒎烯-吡啶的二氯甲烷溶液缓慢加入试管中作为最上层，其中手性单齿含N有机配体L的浓度为0.01~0.02 mol/L；该试管室温下静置4-5天后出现块状无色晶体，过滤，分别用甲醇和水洗涤，室温干燥，即得到(–)-2-(4′-吡啶基)-4,5-蒎烯-吡啶手性银配合物[Ag(L)ClO4] ∞；
所述底层、中间缓冲层和最上层的体积比为（4~7）:（6~9）:（4~7）。
所述步骤(2)中甲醇和二氯甲烷的混合溶液中甲醇和二氯甲烷的体积比为1:2。
所述两种反应物AgClO4与手性单齿含N有机配体L的物质的量之比为1:1。
所述步骤（3）中手性单齿含N有机配体L：(–)-2-(4′-吡啶基)-4,5-蒎烯-吡啶的制备方法如下：
a. 4-(吡啶乙酰基)吡啶碘盐中间体的制备：在250 mL 的圆底烧瓶中，加入5.3克4-乙酰基吡啶，用25~30 mL吡啶溶解，将溶有18~21克碘的20~25 mL吡啶溶液加入圆底烧瓶中，混合物加热至100~110℃，反应4~4.5小时，然后冷却至室温并过滤，用少量的吡啶冲洗二次，真空干燥后得灰色固体即为所需中间体；
b. 手性单齿含N有机配体L：(–)-2-(4′-吡啶基)-4,5-蒎烯-吡啶的合成：称取步骤a制备得到的4.2克4-(吡啶乙酰基)吡啶碘盐中间体以及2.5~3.2克醋酸铵 (NH4Ac) 置于三颈烧瓶中，再加入45~50 mL的甲酰胺(CH3CONH2)。不断搅拌下加入2.8克的桃金娘烯醛(–)-myrtenal (百灵威公司生产)，加热到75-85℃，氮气下反应12-12.5小时，将上述产物过滤得到乳白色固体，并用水冲洗，用乙醇重结晶，然后将固体真空干燥得手性单齿含N有机配体L。
本发明的有益效果：（1）本发明将一种手性单齿含N有机配体L: [(–)-2-(4′-吡啶基)-4,5-蒎烯-吡啶]与AgClO4反应，得到的(–)-2-(4′-吡啶基)-4,5-蒎烯-吡啶手性银配合物的制备方法，工艺简单，常温常压反应，安全性好且成本低，后处理容易且产率高达86%；（2）本发明制备的(–)-2-(4′-吡啶基)-4,5-蒎烯-吡啶手性银配合物不但具有手性光学活性还具有吸收紫外光，产生可见光发射的能力，是极为稀少的同时具有手性光学活性和光转换能力的双功能材料。（3）该手性发光材料具有合成条件温和、产率高、稳定性强、可重现性好、分离纯化容易，有望作为新型发光材料在圆偏振发光、荧光免疫分析、非线性光学材料以及光转换分子器件等方面有广阔的商业化应用前景。
附图说明
图1为实施例1(–)-2-(4′-吡啶基)-4,5-蒎烯-吡啶手性银配合物[Ag(L)ClO4]n的Ag(I)离子配位环境图，为清楚起见，H原子已省略。
图2为实施例1(–)-2-(4′-吡啶基)-4,5-蒎烯-吡啶手性银配合物[Ag(L)ClO4]n的二维层状分子结构图，为清楚起见，H原子已省略。
图3为实施例1(–)-2-(4′-吡啶基)-4,5-蒎烯-吡啶手性银配合物[Ag(L)ClO4]n发光材料的发射光谱图。
图4为实施例1(–)-2-(4′-吡啶基)-4,5-蒎烯-吡啶手性银配合物[Ag(L)ClO4]n发光材料的激发光谱图。
图5为实施例1(–)-2-(4′-吡啶基)-4,5-蒎烯-吡啶手性银配合物[Ag(L)ClO4]n发光材料的手性圆二色光谱图。
具体实施方式
实施例1
本实施例(–)-2-(4′-吡啶基)-4,5-蒎烯-吡啶手性银配合物[Ag(L)ClO4]n的制备方法，步骤如下：
（1）将溶有AgClO4（0.08 mmol，16.6 mg）的甲醇溶液（4 mL）置放在试管的底层；
（2）然后加入6 mL甲醇和二氯甲烷的混合溶液（体积比为CH3OH : CH2Cl2 = 1:2）作为中间缓冲层；
（3）溶有手性单齿含N有机配体L (0.08 mmol，20 mg）的二氯甲烷 (4 mL）作为最上层缓慢加入试管中，该试管室温下静置4-5天后出现块状无色晶体，过滤，分别用甲醇和水洗涤，室温干燥，即得到(–)-2-(4′-吡啶基)-4,5-蒎烯-吡啶手性银配合物[Ag(L)ClO4]n，计算产率为86% (按银计算)。
采用Bruker SMART APEX CCD diffractometer 单晶衍射仪在常温下测定了(–)-2-(4′-吡啶基)-4,5-蒎烯-吡啶手性银配合物[Ag(L)ClO4]n的分子结构 (见图1和图2)。如图2所示，该手性银配合物发光材料的分子结构是由重复单元[Ag(L)ClO4]组成的二维层状结构。利用Biologic MS-500 spectropolarimeter测得了(–)-2-(4′-吡啶基)-4,5-蒎烯-吡啶手性银配合物[Ag(L)ClO4]n的圆二色光谱（见图5），该配合物在波长λ = 253和320 nm处显示负的Cotton效应，证实了该银配合物发光材料的手性光学活性。
(–)-2-(4′-吡啶基)-4,5-蒎烯-吡啶手性银配合物[Ag(L)ClO4]n的发光性能测试：
常温下，利用 FLS980P fluorescence spectrometer 测试了(–)-2-(4′-吡啶基)-4,5-蒎烯-吡啶手性银配合物[Ag(L)ClO4]n的发射和激发光谱（分别对应图3和4）。测试表明：(–)-2-(4′-吡啶基)-4,5-蒎烯-吡啶手性银配合物[Ag(L)ClO4]n在370 nm的紫外光照射下，能发射600 nm的橙红色的荧光。这一结果表明：所制备得到的(–)-2-(4′-吡啶基)-4,5-蒎烯-吡啶手性银配合物[Ag(L)ClO4]n具有大的Stokes位移，能有效吸收紫外光，产生可见光发射，因此，该手性银配合物具有高效的光转换能力，在光转换器件的选择和研制方面具有潜在的应用前景。
本实施例手性单齿含N有机配体L：(–)-2-(4′-吡啶基)-4,5-蒎烯-吡啶的制备方法如下：
a. 4-(吡啶乙酰基)吡啶碘盐中间体的制备：在250 mL 的圆底烧瓶中，加入5.3克4-乙酰基吡啶，用25 mL吡啶溶解，将溶有18克碘的20 mL吡啶溶液加入圆底烧瓶中，混合物加热至100℃，反应4.5小时，然后冷却至室温并过滤，用少量的吡啶冲洗二次，真空干燥后得灰色固体即为所需中间体；
b. 手性单齿含N有机配体L：(–)-2-(4′-吡啶基)-4,5-蒎烯-吡啶的合成：称取步骤a制备得到的4.2克4-(吡啶乙酰基)吡啶碘盐中间体以及2.5克醋酸铵 (NH4Ac) 置于三颈烧瓶中，再加入45 mL的甲酰胺(CH3CONH2)，不断搅拌下加入2.8克的桃金娘烯醛(–)-myrtenal (百灵威公司生产)，加热到75℃，氮气下反应12.5小时，将上述产物过滤得到乳白色固体，并用水冲洗，用乙醇重结晶，然后将固体干燥，得到手性单齿含N有机配体L：(–)-2-(4′-吡啶基)-4,5-蒎烯-吡啶。
产率为87%（按中间体计算）。元素分析：按分子式 C17H18N2（分子量为250.33）：计算值 (%): C, 81.56; H, 7.25; N, 11.19; 实测值 (%): C, 81.51; H, 7.34; N, 11.13。红外光谱 IR (KBr): 2947(s), 2991(m), 2864(v), 1584(m), 1450(s), 1383(m), 782(m), 756(s)。
实施例2
本实施例(–)-2-(4′-吡啶基)-4,5-蒎烯-吡啶手性银配合物[Ag(L)ClO4]n的制备方法，步骤如下：
（1）将溶有AgClO4（0.04 mmol，8.3 mg）的甲醇溶液（4 mL）置放在试管的底层；
（2）然后加入8mL甲醇和二氯甲烷的混合溶液（体积比为CH3OH : CH2Cl2 = 1:2）作为中间缓冲层；
（3）溶有手性单齿含N有机配体L (0.04 mmol，10 mg）的二氯甲烷 (4 mL）作为最上层缓慢加入试管中，该试管室温下静置4-5天后出现块状无色晶体，过滤，分别用甲醇和水洗涤，室温干燥，即得到(–)-2-(4′-吡啶基)-4,5-蒎烯-吡啶手性银配合物[Ag(L)ClO4]n。
本实施例手性单齿含N有机配体L：(–)-2-(4′-吡啶基)-4,5-蒎烯-吡啶的制备方法如下：
a. 4-(吡啶乙酰基)吡啶碘盐中间体的制备：在250 mL 的圆底烧瓶中，加入5.3克4-乙酰基吡啶，用30 mL吡啶溶解，将溶有21克碘的25 mL吡啶溶液加入圆底烧瓶中，混合物加热至110 ℃，反应4.5小时，然后冷却至室温并过滤，用少量的吡啶冲洗二次，真空干燥后得灰色固体即为所需中间体；
b. 手性单齿含N有机配体L：(–)-2-(4′-吡啶基)-4,5-蒎烯-吡啶的合成：称取步骤a制备得到的4.2克4-(吡啶乙酰基)吡啶碘盐中间体以及3.2克醋酸铵 (NH4Ac) 置于三颈烧瓶中，再加入50 mL的甲酰胺(CH3CONH2)，不断搅拌下加入2.8克的桃金娘烯醛(–)-myrtenal (百灵威公司生产)，加热到85℃，氮气下反应12小时，将上述产物过滤得到乳白色固体，并用水冲洗，用乙醇重结晶，然后将固体干燥，得到手性单齿含N有机配体L： (–)-2-(4′-吡啶基)-4,5-蒎烯-吡啶。
实施例3
本实施例(–)-2-(4′-吡啶基)-4,5-蒎烯-吡啶手性银配合物[Ag(L)ClO4]n的制备方法，步骤如下：
（1）将溶有AgClO4（0.08 mmol，16.6 mg）的甲醇溶液（7 mL）置放在试管的底层；
（2）然后加入9 mL甲醇和二氯甲烷的混合溶液（体积比为CH3OH : CH2Cl2 = 1:2）作为中间缓冲层；
（3）溶有手性单齿含N有机配体L (0.08 mmol，20 mg）的二氯甲烷 (6 mL）作为最上层缓慢加入试管中，该试管室温下静置4-5天后出现块状无色晶体，过滤，分别用甲醇和水洗涤，室温干燥，即得到(–)-2-(4′-吡啶基)-4,5-蒎烯-吡啶手性银配合物[Ag(L)ClO4]n。
本实施例手性单齿含N有机配体L：(–)-2-(4′-吡啶基)-4,5-蒎烯-吡啶的制备方法如下：
a. 4-(吡啶乙酰基)吡啶碘盐中间体的制备：在250 mL 的圆底烧瓶中，加入5.3克4-乙酰基吡啶，用28 mL吡啶溶解，将溶有20克碘的24 mL吡啶溶液加入圆底烧瓶中，混合物加热至105℃，反应4.5小时，然后冷却至室温并过滤，用少量的吡啶冲洗二次，真空干燥后得灰色固体即为所需中间体；
b. 手性单齿含N有机配体L：(–)-2-(4′-吡啶基)-4,5-蒎烯-吡啶的合成：称取步骤a制备得到的4.2克4-(吡啶乙酰基)吡啶碘盐中间体以及3.0克醋酸铵 (NH4Ac) 置于三颈烧瓶中，再加入48 mL的甲酰胺(CH3CONH2)，不断搅拌下加入2.8克的桃金娘烯醛(–)-myrtenal (百灵威公司生产)，加热到80℃，氮气下反应12.5小时，将上述产物过滤得到乳白色固体，并用水冲洗，用乙醇重结晶，然后将固体干燥，得到手性单齿含N有机配体L：(–)-2-(4′-吡啶基)-4,5-蒎烯-吡啶。
Claims (4)
1.一种(–)-2-(4′-吡啶基)-4,5-蒎烯-吡啶手性银配合物，所述(–)-2-(4′-吡啶基)-4,5-蒎烯-吡啶手性银配合物的分子式为[Ag(L)ClO4]∞，其中L为手性单齿含N有机配体：(–)-2-(4′-吡啶基)-4,5-蒎烯-吡啶，结构式为
2.根据权利要求1所述的(–)-2-(4′-吡啶基)-4,5-蒎烯-吡啶手性银配合物的制备方法，其特征在于：步骤如下：
(1)将溶有AgClO4的甲醇溶液放入试管中作为底层，其中高氯酸银的浓度为0.01～0.02mol/L；
(2)在底层上加入甲醇和二氯甲烷的混合溶液作为中间缓冲层；
(3)将溶有手性单齿含N有机配体L：(–)-2-(4′-吡啶基)-4,5-蒎烯-吡啶的二氯甲烷溶液缓慢加入试管中作为最上层，其中手性单齿含N有机配体L的浓度为0.01～0.02mol/L；该试管室温下静置4-5天后出现块状无色晶体，过滤，分别用甲醇和水洗涤，室温干燥，得到(–)-2-(4′-吡啶基)-4,5-蒎烯-吡啶手性银配合物[Ag(L)ClO4]∞；
所述底层、中间缓冲层和最上层的液体体积比为(4～7):(6～9):(4～7)；
所述步骤(3)中手性单齿含N有机配体L：(–)-2-(4′-吡啶基)-4,5-蒎烯-吡啶的制备方法如下：
a.4-(吡啶乙酰基)吡啶碘盐中间体的制备：在250mL的圆底烧瓶中，加入5.3克4-乙酰基吡啶，用25～30mL吡啶溶解，将溶有18～21克碘的20～25mL吡啶溶液加入圆底烧瓶中，混合物加热至100～110℃，反应4～4.5小时，然后冷却至室温并过滤，用少量的吡啶冲洗二次，真空干燥后得灰色固体即为所需中间体；
b.手性单齿含N有机配体L：(–)-2-(4′-吡啶基)-4,5-蒎烯-吡啶的合成：称取步骤a制备得到的4.2克4-(吡啶乙酰基)吡啶碘盐中间体以及2.5～3.2克醋酸铵置于三颈烧瓶中，再加入45～50mL的甲酰胺，不断搅拌下加入2.8克的桃金娘烯醛(–)-myrtenal，加热到75-85℃，氮气下反应12-12.5小时，将上述产物过滤得到乳白色固体，并用水冲洗，用乙醇重结晶，然后将固体真空干燥得手性单齿含N有机配体L。
3.根据权利要求2所述的(–)-2-(4′-吡啶基)-4,5-蒎烯-吡啶手性银配合物的制备方法，其特征在于：所述步骤(2)中甲醇和二氯甲烷的混合溶液中甲醇和二氯甲烷的体积比为1:2。
4.根据权利要求2所述的(–)-2-(4′-吡啶基)-4,5-蒎烯-吡啶手性银配合物的制备方法，其特征在于：所述AgClO4与手性单齿含N有机配体L的物质的量之比为1:1。
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