CN102277155A - 一种有机白光发射材料l-cooh的制备和用途 - Google Patents

一种有机白光发射材料l-cooh的制备和用途 Download PDF

Info

Publication number
CN102277155A
CN102277155A CN201110176861A CN201110176861A CN102277155A CN 102277155 A CN102277155 A CN 102277155A CN 201110176861 A CN201110176861 A CN 201110176861A CN 201110176861 A CN201110176861 A CN 201110176861A CN 102277155 A CN102277155 A CN 102277155A
Authority
CN
China
Prior art keywords
preparation
white light
cooh
organic
pyridyl
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN201110176861A
Other languages
English (en)
Other versions
CN102277155B (zh
Inventor
张�杰
金旭辉
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Fujian Institute of Research on the Structure of Matter of CAS
Original Assignee
Fujian Institute of Research on the Structure of Matter of CAS
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Fujian Institute of Research on the Structure of Matter of CAS filed Critical Fujian Institute of Research on the Structure of Matter of CAS
Priority to CN201110176861.1A priority Critical patent/CN102277155B/zh
Publication of CN102277155A publication Critical patent/CN102277155A/zh
Application granted granted Critical
Publication of CN102277155B publication Critical patent/CN102277155B/zh
Expired - Fee Related legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02B—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO BUILDINGS, e.g. HOUSING, HOUSE APPLIANCES OR RELATED END-USER APPLICATIONS
    • Y02B20/00—Energy efficient lighting technologies, e.g. halogen lamps or gas discharge lamps

Landscapes

  • Pyridine Compounds (AREA)

Abstract

本发明属于发光与显示技术领域，涉及一种有机白光发射材料L-COOH的制备和用途。该材料化学式为[C28H21N4O2]·ClO4，其主体为4′-(N-(4-羧基-苯亚甲基)-4-吡啶基)-2,2′:6′,2′'-三联吡啶鎓，另一部分为平衡阴离子ClO4 –。其中平衡阴离子可以被Cl–、NO3 –、PF6 –、BF4 –等置换。L-COOH的分子量为544.94。采用亲核取代法制备。其晶体或薄膜在400－750nm范围内存在双发射，在365nm的紫外灯激发下可发射白光。该材料改善了有机多分子混合材料稳定性不高，容易相分离以及需要较高制备工艺等缺点，可用于白光LED的制备及其它发光显示领域。

Description

一种有机白光发射材料L-COOH的制备和用途
技术领域
本发明涉及有机白光发射材料4′-(N-(4-羧基-苯亚甲基)-4-吡啶基)- 2,2′:6′,2′'-三联吡啶鎓盐L-COOH的制备和应用。
背景技术
有机白光发射材料的设计与合成近年来一直是OLED材料研发的焦点。其中，由于有机多分子混合材料具有稳定性不高，容易相分离，以及需要较高制备工艺等缺点，稳定的有机单分子白色荧光材料的研发日益受到关注。然而由于白光为复合光，通常是由红色，黄色，蓝色三原色或者蓝光和黄光相混合形成，所以到目前为止具有稳定白色荧光的有机单分子非常少见，而且几乎所有报道都集中在溶液中。众所周知，有机分子在固体中由于其构型及堆积的影响其荧光发光性质往往与溶液中不同，所以开发在固态中稳定的有机白色荧光材料至关重要。
目前，所报导的合成固态白光有机分子材料最典型的策略为激基复合物策略。也就是利用自身具有蓝色荧光的有机分子通过堆积产生分子间的激基复合物从而在固态中产生双色荧光发射，复合后产生白光。然而这样所产生的长波荧光发射往往受堆积影响较大，分子之间堆积距离的改变就可以造生长波发射波长的移动甚至淬灭，在实际合成中很难控制。为了克服这一缺点，我们合成了一种新型的鎓盐分子，通过修饰取代基基团调控分子内电荷转移作用的强弱，成功实现了分子的白光发射。
发明内容
本发明的目的在于制备一种有机白光发射材料4′-(N-(4-羧基-苯亚甲基)-4-吡啶基)- 2,2′:6′,2′'-三联吡啶鎓盐，简写为L-COOH。其
技术方案如下：
我们选择4′-(4-吡啶基)-2,2':6′,2′′-三联吡啶与对氯甲基苯甲酸为原料，其摩尔比为1:3，采用乙腈作溶剂，通过亲核取代反应制得一氯化4′-(N-(4-羧基-苯亚甲基)-4-吡啶基)-2,2′:6′,2′'-三联吡啶鎓(L-COOH·Cl)。随后通过离子交换制得L-COOH·ClO4。其红外光谱的主要振动吸收如下(KBr，cm– 1): 1700(m), 1637(s), 1583(m), 1547(s), 1523(m), 1473(m), 1393(s), 1345(w), 1267(w), 1236(w), 1154(m), 1117(s), 1085(s), 998(w), 852(m), 790(s), 764(s), 624(m), 511(m).
此外，我们还通过X-射线单晶衍射技术测定了化合物L-COOH·ClO4的结构，其结构参数如下：分子式C28H21N4ClO6，分子量544.94, 单斜晶系，空间群C2/c，晶胞参数为a = 15.5649(16), b = 11.7644(11)，c = 27.387(2) Å，β = 93.531(7)°, V = 5006.2(8) Å3，Z = 8。其结构式如下：
Figure 2011101768611100002DEST_PATH_IMAGE001
荧光光谱测量表明，L-COOH·ClO4具有良好的发光性能，除了在441 nm处有一个强的荧光发射外，在557 nm处还有一个较宽的强度约为441 nm发射峰一半的荧光发射峰。整个荧光发射谱带的带宽为400-750nm，几乎包括整个可见光区。按照国际照明协会(CIE)的标准计算得到其荧光发射的色度坐标为(0.304, 0.235)，在365nm的紫外灯下可表现为明亮的白色。
本发明所采用的材料制备方法具有工艺简单、产率高及稳定性好等优点。可用于白光LED的制备及其它发光、显示领域。可通过离子交换，将ClO4 –平衡阴离子置换为Cl–、NO3 –、PF6 –、BF4 –等对发光性能进行调控，用于发光与显示技术领域。
具体实施方式
、化合物的制备
将0.16 g 4′-(4-吡啶基)-2,2':6′,2′′-三联吡啶分子和0.264 g 对氯甲基苯甲酸溶于20 mL乙腈中，然后加入到圆底烧瓶中加热回流约24 h，当反应液冷却后有白色沉淀产生，过滤烘干后得到白色粉末状产物L-COOH·Cl。
称取30 mg L-COOH·Cl样品和80 mg LiClO4加入到3 mL磷酸钠缓冲溶液(NaH2PO4: NaH2PO4=1:1)中, 搅拌后将混合溶液加入含有聚四氟乙烯内胆的不锈钢反应釜中，加热至110 ºC恒温3天，之后在3天内降至室温，得到淡黄色棱柱状晶体L-COOH·ClO4。
2、性能测试
我们对L-COOH·ClO4晶体及PVP薄膜进行了荧光光谱测试测试，在365 nm的激发波长下，按国际照明协会(CIE)的标准计算其荧光发射的色度坐标分别为(0.304，0.235)和(0.302，0.310)，在白光范围之内。

Claims (4)

1.一种有机白光发射材料，该材料为4′-(N-(4-羧基-苯亚甲基)-4-吡啶基)-2,2′:6′,2′'-三联吡啶鎓盐，特征在于:其化学式为[C28H21N4O2]·ClO4，分子量为544.94，其结构式为:
Figure 2011101768611100001DEST_PATH_IMAGE001
。
2.一种权利要求1的有机白光发射材料的制备方法，其特征在于：4′-(4-吡啶基)-2,2’:6′,2′′-三联吡啶与对氯甲基苯甲酸为原料，通过亲核取代反应制备。
3.一种权利要求1的有机白光发射材料的用途，其特征在于将该材料用于发光与显示技术领域。
4.一种权利要求1的有机白光发射材料的用途，其特征在于通过离子交换，将ClO4 –平衡阴离子置换为Cl–、NO3 –、PF6 –、BF4 –等对发光性能进行调控并用于发光与显示技术领域。
CN201110176861.1A 2011-06-28 2011-06-28 一种有机白光发射材料l-cooh的制备和用途 Expired - Fee Related CN102277155B (zh)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201110176861.1A CN102277155B (zh) 2011-06-28 2011-06-28 一种有机白光发射材料l-cooh的制备和用途

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201110176861.1A CN102277155B (zh) 2011-06-28 2011-06-28 一种有机白光发射材料l-cooh的制备和用途

Publications (2)

Publication Number Publication Date
CN102277155A true CN102277155A (zh) 2011-12-14
CN102277155B CN102277155B (zh) 2014-10-15

Family

ID=45102897

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201110176861.1A Expired - Fee Related CN102277155B (zh) 2011-06-28 2011-06-28 一种有机白光发射材料l-cooh的制备和用途

Country Status (1)

Country Link
CN (1) CN102277155B (zh)

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1407052A (zh) * 2001-08-22 2003-04-02 中国科学院大连化学物理研究所 新型稀土荧光标记物及其应用
CN1685232A (zh) * 2002-03-08 2005-10-19 松本和子 新型荧光标识化合物
CN1746258A (zh) * 2005-09-23 2006-03-15 中国科学院长春应用化学研究所 合成含有三联吡啶钌的微米及纳米粒子的方法
CN1784454A (zh) * 2002-11-06 2006-06-07 香港大学 具有基于三联吡啶基团的电致发光金属－超分子
CN1811430A (zh) * 2005-01-26 2006-08-02 中国科学院大连化学物理研究所 一种单线态氧铕配合物荧光探针及其应用
CN101544673A (zh) * 2009-04-24 2009-09-30 大连理工大学 以不同长度饱和碳链连接的双核联吡啶钌/锇ecl标示物

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1407052A (zh) * 2001-08-22 2003-04-02 中国科学院大连化学物理研究所 新型稀土荧光标记物及其应用
CN1685232A (zh) * 2002-03-08 2005-10-19 松本和子 新型荧光标识化合物
CN1784454A (zh) * 2002-11-06 2006-06-07 香港大学 具有基于三联吡啶基团的电致发光金属－超分子
CN1811430A (zh) * 2005-01-26 2006-08-02 中国科学院大连化学物理研究所 一种单线态氧铕配合物荧光探针及其应用
CN1746258A (zh) * 2005-09-23 2006-03-15 中国科学院长春应用化学研究所 合成含有三联吡啶钌的微米及纳米粒子的方法
CN101544673A (zh) * 2009-04-24 2009-09-30 大连理工大学 以不同长度饱和碳链连接的双核联吡啶钌/锇ecl标示物

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
XU-HUI JIN ET AL.: "pH-induced coordination assembly of mononuclear and dinuclear copper(II) complexes based on a 4,4′-bipyridinium analogue", 《INORGANIC CHEMISTRY COMMUNICATIONS》 *

Also Published As

Publication number Publication date
CN102277155B (zh) 2014-10-15

Similar Documents

Publication Publication Date Title
Lou et al. Enhanced Solution and Solid‐State Emission and Tunable White‐Light Emission Harvested by Supramolecular Approaches
CN109370569B (zh) 一种含碳量子点白光发射室温离子液体的制备方法
CN110041351B (zh) 一种含邻菲啰啉、修饰咪唑羧酸和吡啶羧酸混合配体的Er(III)发光材料及制备方法
Liu et al. Organocounterions-assisted and pH-controlled self-assembly of five nanoscale high-nuclear lanthanide substituted heteropolytungstates
Tan et al. Carbazole-based highly solid-state emissive fluorene derivatives with various mechanochromic fluorescence characteristics
CN103254892B (zh) 一种固态宽带蓝光发射有机发光材料及其制备方法
CN105542751B (zh) 一种发射白光的金属有机框架材料及其合成方法和应用
Zhou et al. Diverse lanthanide coordination polymers tuned by the flexibility of ligands and the lanthanide contraction effect: syntheses, structures and luminescence
Li et al. Synthesis, crystal structure and optical property of manganese (II) halides based on pyridine ionic liquids with high quantum yield
Li et al. Aggregation-induced phosphorescent emission-active Ir (iii) complexes with a long lifetime for specific mitochondrial imaging and tracking
Gupta et al. Utilizing a series of fac-Re (CO) 3 core based quinonoid containing complexes for photophysical and cell imaging studies
Jiang et al. A fluorescence/phosphorescence dual-emitting metal-organic framework exhibiting two approaches for single-phase white-light emission
CN107892703A (zh) 一种双核有机金属配合物及其应用
Xu et al. Design, synthesis and characterization of a highly luminescent Eu-complex monomer featuring thenoyltrifluoroacetone and 5-acryloxyethoxymethyl-8-hydroxyquinoline
CN105001141B (zh) 一种氟代苯基吲哚类化合物，其作为红色有机发光材料的应用及其制备方法
Zhang et al. Dual-sensitized Eu (III)/Tb (III) complexes exhibiting tunable luminescence emission and their application in cellular-imaging
CN105837568B (zh) 一种芴基β‑咔啉类化合物，其作为有机发光材料和聚集诱导荧光增强材料的应用及制备方法
CN109336932B (zh) 两亲性铂(ⅱ)配合物及其制备和构筑白色发光体系的应用
CN102719237B (zh) 一种Zn(II)配合物发光材料及其制备方法
CN102277155B (zh) 一种有机白光发射材料l-cooh的制备和用途
Ding et al. Single-phase white light material and antibiotic detection of lanthanide metal–organic frameworks
CN110551292A (zh) 一种光色可调的稀土发光材料的制备方法
CN112175607B (zh) 有机室温磷光材料及其制备方法和应用
Yu et al. Through-bond/space conjugated nonaromatic dihydrobenzoquinolines: Luminogens with simple synthesis method, strong aggregation-induced emission and emissive excimers
CN102329264B (zh) 一种有机白光发射材料L-Cl的制备和用途

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant
CF01 Termination of patent right due to non-payment of annual fee
CF01 Termination of patent right due to non-payment of annual fee

Granted publication date: 20141015

Termination date: 20190628