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I SYNTHESIS of LIGANDS and MACROCYCLES BASED on 1,3 SYNTHESIS OF LIGANDS AND MACROCYCLES BASED ON 1,3- DIIMINOISOINDOLINES AND STUDY OF NEW HIGHLY FLUORESCENT AND SYMMETRIC PYRROLE-BF2 CHROMOPHORES A Dissertation Presented to The Graduate Faculty of The University of Akron In Partial Fulfillment of the Requirements for the Degree Doctor of Philosophy Ingrid-Suzy Tamgho December, 2014 i SYNTHESIS OF LIGANDS AND MACROCYCLES BASED ON 1,3- DIIMINOISOINDOLINES AND STUDY OF NEW HIGHLY FLUORESCENT AND SYMMETRIC PYRROLE-BF2 CHROMOPHORES Ingrid-Suzy Tamgho Dissertation Approved: Accepted: ________________________ ________________________ Advisor Department Chair Dr. Christopher J. Ziegler Dr. Kim Calvo ________________________ ________________________ Committee Member Dean of the College Dr. Claire A. Tessier Dr. Chand Midha ________________________ ________________________ Committee Member Dean of the Graduate School Dr. Michael J. Taschner Dr. George Newkome ________________________ ________________________ Committee Member Date Dr. Yi Pang ________________________ Committee Member Dr. Kevin A. Cavicchi ii ABSTRACT Discovered in 1907 by Braun and Tcherniac, a phthalocyanine is a macrocycle composed of four isoindolines. The metal chemistry of this macrocycle is rich, as of today, the phthalocyanines are well-known dyes and photosensitizers. Among the variety of phthalocyanine precursors, 1,3-diiminoisoindoline and phthalonitrile are the most widely used. Indeed, new macrocyles and ligands are synthesized from these compounds, either by condensation of 1,3-diiminoisoindoline or the CaCl2-catalyzed reaction of phthalonitrile with an amine. Following these methods, we are able to prepare a series of compounds, the phthalocrown, and also revisit the chemistry of bis(alkylimino)isoindolines. The first part of the dissertation describes the synthesis and characterization of phthalocrowns. They can be considered as chimera molecules composed of a crown ether and phthalocyanine. These compounds are synthesized via Schiff base-type condensation reactions between polyetherdiamines and 1,3-diiminoisoindoline, which can be generated from phthalonitrile. Secondly, we revisit the chemistry of bis(alkylimino)isoindolines. These compounds can be generated via phthalonitrile and 1,3-diiminoisoindoline depending on the nature of the amine. Also, the metal chemistry of these compounds with Ag(I) is described. iii One important class of fluorescent dyes is known as BODIPY. This fluorophore consists of a dipyrromethene bound to a central BF2 unit. The compound is found to possess excellent photophysical properties such as high extinction coefficient and high quantum yield of emission. Moreover, BODIPY is insensitive to pH and solvent polarity and is photostable. Its versatility, introduced via the attachment of biomolecules or other moieties, allows these dyes to have important applications from biological imaging and sensing to light harvesting. In the final chapter, we discuss the synthesis of a novel family of fluorophores, the BOPHY. These dyes are synthesized via the Schiff-base reaction of a pyrrole carbaldehyde with hydrazine, followed with a BF2 complexation to yield highly fluorescent chromophores. The BOPHY optical properties are discussed in the final chapter as well. iv DEDICATION To my parents, my sister and brother La vraie magie c’est le travail v ACKNOWLEDGEMENTS First, I would like to thank God (Gue fuote Tchiepo Si). “I could have never made it without you. When I look back over what you brought me through, I realize that I made it because I had You to hold on to”. I would also like to gratefully and sincerely thank my advisor Dr. Christopher J. Ziegler for he is a great teacher, mentor and advisor. His guidance, his encouragement and patience made me become the confident scientist that I am today. To Kullapa, Abed, Laura, Allen, Anthony, Roshinee, Jim, Sarah and Nada, I will always be thankful for your friendship, help and support. You made working in the lab an enjoyable experience. I will miss working with you guys. I would like to acknowledge the department of Chemistry for giving me the opportunity to study in this university and financial support during these years. I will extend my thanks to Dr. Pang, Dr. Taschner, Dr. Tessier and Dr. Cavicchi from the Polymer Engineering department for taking time to serve in my committee. Your helpful suggestions and advice were preciously appreciated and I am grateful that you considered me as being qualified to earn my Ph.D in chemistry. Being an ocean away from home is not easy, I was lucky enough to meet friends in and outside the university that made me feel Akron as my second home. I would not be able to name all of you here, but you definitely know who you are. vi A mon petit frère, Teddy et ma grande sœur, Stéphanie, cette dissertation est pour vous. Sans vous, je n’aurais pu jamais finir cette dissertation. Maman nous a toujours dit de prendre exemple sur nos ainés. Stéphanie, j’ai la chance de t’avoir comme grande sœur et meilleure amie. Tu as toujours été présente, tu m’as toujours supportée et voulu le meilleur pour nous tes petits (Teddy et moi). Teddy, petit, tu es aussi ma source d’inspiration et de motivation. Tu m’as montré que pour réussir et être le meilleur, il faut savoir se sacrifier et travailler très dur. Merci à vous, pour le soutien moral et financier (hiiiii), j’espère que vous êtes fiers de votre petite (grande) sœur. A mes parents, Alice et Jean-Bosco, sans qui je ne serais pas la. Je vous remercie du fond du cœur. Motokoua. vii TABLE OF CONTENTS Page LIST OF TABLES ...............................................................................................................x LIST OF FIGURES .......................................................................................................... xii LIST OF SCHEMES..........................................................................................................xv LIST OF ABBREVIATIONS ......................................................................................... xvii CHAPTER I. INTRODUCTION AND BACKGROUND ............................................................1 1.1 Introduction to DII and DII-based ligands ............................................................1 1,3-diiminoisoindoline .................................................................................4 Chemistry of 1,3-diiminoisoindoline ...........................................................9 Oxime-DII ..................................................................................................10 Phthalazines ...............................................................................................11 1,1,3-trichloroisoindoline ...........................................................................14 3-imino-1-oxoisoindoline ..........................................................................15 Coordinating Bis(arylimino)isoindolines - 1,3-Bis(2-pyridylimino)isoindoline ..........................................................22 Alternative coordinating bis(arylimino)isoindolines .................................33 Non-coordinating Bis(arylimino)isoindolines ...........................................34 Bis(alkylimino)isoindolines .......................................................................36 1.2 BF2-based fluorophores ......................................................................................37 Fluorescence ..............................................................................................38 viii Classes of fluorophores ..............................................................................40 BODIPY .....................................................................................................45 Aza-BODIPY .............................................................................................54 BODIPY analogues ....................................................................................58 II. THE PHTHALOCROWNS: ISOINDOLINE-CROWN ETHER MACROCYCLES ....................................................................................63 Experimental ..............................................................................................65 Results and Discussion ..............................................................................71 III. THE SYNTHESES AND STRUCTURES OF BIS(ALKYLIMINO)ISOINDOLINES .................................................................78 Experimental ..............................................................................................82 Results and Discussion ............................................................................105 IV. A NEW HIGHLY FLUORESCENT AND SYMMETRIC PYRROLE-BF2 CHROMOPHORE: BOPHY ....................................................118 Experimental ............................................................................................119 Results and Discussion ............................................................................127 V. SUMMARY .........................................................................................................142 REFERENCES ................................................................................................................146 APPENDIX ......................................................................................................................161 ix LIST OF TABLES Table Page 2.1 Crystal data and structure refinement for 4-mono ............................................. 68 2.2 Crystal data and structure refinement for 4-ortho ............................................
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