CN111793828A - 一种有机苯并噻唑类晶体材料及其制备方法 - Google Patents
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Abstract
本发明属于功能晶体材料合成技术领域,涉及一种有机苯并噻唑类晶体材料及其制备方法,所述有机苯并噻唑类晶体材料为2‑(4‑二甲基氨基)苯乙烯基‑苯并噻唑,其化学式为C17H16NS,原料易得,制备方法简单,制备的晶体结构中带有苯并噻唑环的分子,苯并噻唑环上具有优异的π电子共轭体系,使得整个晶体分子结构中形成较大的π电子共轭体系,非中心对称性显著提高,有利于产生较大的非线性光学系数,其二阶非线性光学性质是KDP的29倍,非线性性能较好,同时还具有荧光发射性质,具有较高的潜在实用价值。
Description
技术领域:
本发明属于功能晶体材料合成技术领域,涉及一种有机非线性光学晶体材料及其制备方法,特别是一种有机苯并噻唑类晶体材料及其制备方法。
背景技术:
有机非线性晶体具有较大的二阶非线性光学系数、较高的电光系数以及较低的介电常数,其转换效率高、带宽大、相位匹配条件简单,在高效太赫兹波的产生与探测、光电转换、电光取样、毫米波监测、倍频及光学参数发生等方面具有广阔的应用前景。有机晶体在作为太赫兹发射源时产生的频谱宽度能覆盖整个太赫兹波段(0.1-10THz),且太赫兹脉冲短,飞行时间分辨率高,成本低;另外,有机晶体结构易裁剪,设计空间大,电子响应速度快,能满足未来超高宽带光子器件的使用需求。
有机THz晶体目前主要分为吡啶盐体系、喹啉体系和苯并噻唑体系,其中以吡啶基团为电子受体的吡啶盐体系有机晶体是一种重要的非线性材料。1989年,美国学者S.R.Marder首次报道吡啶盐体系的有机盐DAST(4-(4-二甲基氨基苯乙烯基甲基吡啶对甲苯磺酸盐),它是一种具有高二阶非线性系数和低介电常数的有机晶体,能产生高效的THz波,但是高质量、大尺寸DAST晶体的生长工艺尚不成熟,且晶体稳定性较差,易与水形成不具有THz性能的DAST·H2O,另外在泵浦光-THz波转换过程中,在1.1THz处有较强的吸收。对于喹啉体系的晶体,目前最好的是HMQ-T晶体,该晶体具有较大的非线性系数和接近理想的分子取向参数,因此,生长的HMQ-T晶体不需要任何抛光和切割,可直接用作THz波辐射源材料。此外,喹啉体系其它衍生物OHQ-T、HMQ-TMS、OHQ-TFO等晶体也因良好的环境稳定性和耐湿性,受到广泛关注。喹啉体系的晶体当中:诸如OHQ-T晶体目前需要在甲醇与乙腈的混合溶剂中生长;而OHQ-VBS目前没有较大尺寸的晶体;OHQ-I只能生长出细针状的晶体而无法实际应用;性能比较好的OHQ-TFO晶体却是通过“有限几何”的方法才能生长出较薄的单晶。就喹啉体系的晶体来说,较难生长大尺寸、高质量的单晶,是目前亟需解决的问题。
相比于吡啶盐体系和喹啉体系晶体,苯并噻唑体系晶体具有更强的电子吸附能力,能促进晶体间电荷的转移,增大晶体非线性效应,比如HDB-T、PMB-T、HMB-T等苯并噻唑系列晶体,具有较好的太赫兹性能,能弥补吡啶盐类晶体在1.1THz处的强吸收,且不易潮解。
发明内容:
本发明的目的在于克服现有有机THz晶体材料物理化学性能上的不足,提供一种新型有机苯并噻唑类晶体材料及其制备方法,制备的晶体SHG强度较强,是KDP晶体的29倍。
为了实现上述目的,本发明所述有机苯并噻唑类晶体材料为2-(4-二甲基氨基)苯乙烯基-苯并噻唑,其化学式为C17H16NS,简称:DAB,其结构式为:
本发明所述有机苯并噻唑类晶体材料的制备过程包括以下步骤:
(1)将0.5~2mol的4-氯苯磺酰氯溶解在50~100ml的甲醇溶液中,搅拌、溶解;
(2)将0.5~2mol的甲醇钠溶解在80~160ml的甲醇溶液中,搅拌、溶解;
(3)将步骤(1)和步骤(2)中得到的溶液置于带有冷凝回流装置的三口烧瓶中,加入磁子搅拌,45~55℃油浴加热,反应24~36h;
(4)向步骤(3)得到的溶液中加入0.5~2mol的2-甲基苯并噻唑和25~50ml的甲醇,55~65℃条件下反应24~36h;
(5)将0.5~2mol的对二甲基氨基苯甲醛溶解在55~110ml的甲醇溶液中,然后将得到的溶液置于步骤(4)溶液中,同时加入催化剂,在65~75℃下反应3~5天,得深红色溶液;
(6)将步骤(5)得到的溶液重结晶3~5次,得黄色晶体生长原料;
(7)将步骤(6)得到的黄色晶体生长原料溶解在甲醇中,抽滤,置于能够控温的育晶瓶当中,0.5~1℃/天的速率降温,15~40天后获得黄色2-(4-二甲基氨基)苯乙烯基-苯并噻唑晶体。
本发明所述4-氯苯磺酰氯的纯度>98%,甲醇钠的纯度>97%,2-甲基苯并噻唑的纯度>98%,对二甲氨基苯甲醛的纯度>95%,无水甲醇的纯度>99.5%。
本发明与现有技术相比,原料易得,制备方法简单,制备的晶体结构中带有苯并噻唑环的分子,苯并噻唑环上具有优异的π电子共轭体系,使得整个晶体分子结构中形成较大的π电子共轭体系,非中心对称性显著提高,有利于产生较大的非线性光学系数,其二阶非线性光学性质是KDP的29倍,非线性性能较好,同时还具有荧光发射性质,具有较高的潜在实用价值。
附图说明:
图1为本发明所得DAB晶体生长原料图。
图2为本发明所得DAB晶体图。
图3为本发明所得DAB晶体的单晶XRD衍射图。
图4为本发明所得DAB粉末的XRD衍射图样与理论计算XRD衍射图样。
图5为本发明所得DAB与KDP二次谐波信号强度对比图。
具体实施方式:
下面通过实施例并结合附图对本发明作进一步说明。
实施例:
(1)将10.55g(0.5mol)4-氯苯磺酰氯溶解在50ml的甲醇(99.5%)溶液中,搅拌、溶解;
(2)将2.7g(0.5mol)甲醇钠溶解在80ml的甲醇(99.5%)溶液中,搅拌、溶解;
(3)将步骤(1)和步骤(2)中得到的溶液置于带有冷凝回流装置的三口烧瓶中,加入磁子搅拌,45℃油浴加热,反应36h;
(4)向步骤(3)得到的溶液中加入6.35ml(0.5mol)的2-甲基苯并噻唑和25ml的甲醇,60℃反应24h;
(5)将7.45g(0.5mol)对二甲基氨基苯甲醛溶解在55ml的甲醇溶液中,然后将得到的溶液置于步骤(4)得到的溶液中,同时加入催化剂,在70℃下反应3天,得深红色的溶液;
(6)将步骤(5)中得到的溶液重结晶3次,得黄色晶体生长原料DAB,如图1所示;
(7)将步骤(6)得到的DAB原料溶解在甲醇中,抽滤,置于能够控温的育晶瓶当中,1℃/天的速率降温,20天后获得黄色DAB晶体,如图2所示,对制备的DAB晶体进行单晶衍射实验,其结果如图3和图4所示,将DAB与KDP二次谐波信号强度进行对比,其结果如图5所示,DAB二阶非线性光学性质是KDP的29倍。
Claims (4)
3.一种如权利要求2所述有机苯并噻唑类晶体材料的制备方法,其特征在于制备过程包括以下步骤:
(1)将0.5~2mol的4-氯苯磺酰氯溶解在50~100ml的甲醇溶液中,搅拌、溶解;
(2)将0.5~2mol的甲醇钠溶解在80~160ml的甲醇溶液中,搅拌、溶解;
(3)将步骤(1)和步骤(2)中得到的溶液置于带有冷凝回流装置的三口烧瓶中,加入磁子搅拌,45~55℃油浴加热,反应24~36h;
(4)向步骤(3)得到的溶液中加入0.5~2mol的2-甲基苯并噻唑和25~50ml的甲醇,55~65℃条件下反应24~36h;
(5)将0.5~2mol的对二甲基氨基苯甲醛溶解在55~110ml的甲醇溶液中,然后将得到的溶液置于步骤(4)溶液中,同时加入催化剂,在65~75℃下反应3~5天,得深红色溶液;
(6)将步骤(5)得到的溶液重结晶3~5次,得黄色晶体生长原料;
(7)将步骤(6)得到的黄色晶体生长原料溶解在甲醇中,抽滤,置于能够控温的育晶瓶当中,0.5~1℃/天的速率降温,15~40天后获得黄色2-(4-二甲基氨基)苯乙烯基-苯并噻唑晶体。
4.根据权利要求3所述有机苯并噻唑类晶体材料的制备方法,其特征在于所述4-氯苯磺酰氯的纯度>98%,甲醇钠的纯度>97%,2-甲基苯并噻唑的纯度>98%,对二甲氨基苯甲醛的纯度>95%,无水甲醇的纯度>99.5%。
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Cited By (2)
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CN112279818A (zh) * | 2020-11-12 | 2021-01-29 | 青岛大学 | 一种2-(4-羟基)-苯乙烯基-5-氯苯并噻唑对甲苯磺酸盐的制备方法 |
CN113293439A (zh) * | 2021-04-22 | 2021-08-24 | 青岛大学 | 一种有机非线性光学晶体材料dobt及其制备方法 |
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Cited By (2)
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CN112279818A (zh) * | 2020-11-12 | 2021-01-29 | 青岛大学 | 一种2-(4-羟基)-苯乙烯基-5-氯苯并噻唑对甲苯磺酸盐的制备方法 |
CN113293439A (zh) * | 2021-04-22 | 2021-08-24 | 青岛大学 | 一种有机非线性光学晶体材料dobt及其制备方法 |
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