Функционализированные 5-арил-2,2`-бипиридины и их люминесцентные комплексы с лантанидами(III) тема диссертации и автореферата по ВАК РФ 02.00.03, кандидат химических наук Копчук, Дмитрий Сергеевич

• Копчук, Дмитрий Сергеевич
• кандидат химических наук
• 2010

Оглавление диссертации кандидат химических наук Копчук, Дмитрий Сергеевич

Введение.

1 Литературный обзор.

1.1 Люминесцентные комплексы катионов лантанидов.

1.1.1 Общие принципы построения лигандов для катионов лантанидов, применяемых для создания фосфоресцентных меток.

1.1.2 Применение комплексов лантанидов для создания OLED.

1.2 Люминесцентные индикаторы на катионы цинка(И).

1.2.1 Принципы PET и ICT.

1.2.2 Примеры индикаторов, использующих РЕТ-принцип.

1.2.3 Примеры индикаторов, использующих 1СТ-принцип.

Введение диссертации (часть автореферата) на тему «Функционализированные 5-арил-2,2`-бипиридины и их люминесцентные комплексы с лантанидами(III)»

Люминесцентные комплексы лантанидов и функционализированных гетероциклов находят широкое применение при создании новых материалов: от меток для фосфоресцентного иммуноанализа до люминофоров для органических светодиодов. Несмотря на то, что люминесценция таких комплексов связана с электронными переходами самого атома лантанида, целевые характеристики, которыми должен обладать материал (поглощение света, связывание с белками, растворимость, летучесть, стабильность и т.д.), практически полностью определяются именно строением гетероциклической составляющей. Зачастую требуется тонкая настройка структуры лиганда для достижения разных по своей природе свойств комплекса. В ряде случаев это становится нетривиальной задачей, для решения которой нужны новые лиганды, а значит, и новые методы для их синтеза и функционализации, что и определяет актуальность данной работы.

В основе большинства лигандов для люминесцентных лантанидных комплексов лежит пиридиновое (би- и терпиридиновое) ядро, которое обеспечивает перенос энергии возбуждения от лиганда к металлу. Необходимым условием для получения комплексов с заданными свойствами является наличие дополнительных координационных центров (карбоксилатных, карбонильных групп, остатков олигоэтиленаминов, иминоуксусной кислоты и др.), которые отвечают за стабильность, заряд, растворимость координационного соединения лантанида и т.п. Настройка фотофизических свойств может достигаться введением ароматических заместителей. Учитывая, что для получения комплексов различных лантанидов могут быть использованы лиганды одной группы, разрабатываемые подходы должны давать возможность варьирования заместителей для подстройки свойств и структуры лиганда под конкретный металл.

Цель работы - поиск методов синтеза функционализированных бипиридинов для получения люминесцентных лантанидных комплексов с возможностью настройки свойств комплексов за счет варьирования структуры лиганда. Задачи:

1. Поиск синтетических подходов к 5-арил-2,2'-бипиридинкарбоновым кислотам -лигандам для получения нейтральных комплексов лантанидов, управление их свойствами за счет варьирования заместителей в лиганде.

2. Поиск новых лигандов для устойчивых Eu(III) хелатов на основе 5-арил-2,2'-бипиридинов, несущих остатки олигоэтиленаминоуксусных кислот - хромофоров для меток для фосфоресцентного иммуноанализа.

1 Литературный обзор

Литературный обзор посвящен устойчивым люминесцентным лантанидным комплексам. Вследствие разных сфер применения лантанидных хелатов различные требования предъявляются и к структуре лигандов. В рамках данного обзора рассмотрены общие требования к построению лигандов для дальнейшего создания на их основе фосфоресцентных меток для иммуноанализа (в первую очередь внимание уделяется лигандам пиридинового ряда как объекту исследования данной работы), отдельно рассмотрены комплексы лантанидов, используемые для создания электролюминесцентных материалов. В соответствие с тематикой данной работы в состав обзора включен раздел, посвященный флюоресцентным сенсорам на катионы цинка.

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