Squaric acid as a versatile compound in the design of molecular solids [Elektronische Ressource] / vorgelegt von Mihaela Diana Serb, geb. Durigu

Informations

• Publié par: rheinisch-westfalischen_technischen_hochschule_-rwth-_aachen
• Publié le: 01 janvier 2008
• Nombre de lectures: 179
• Poids de l'ouvrage: 23 Mo

Extrait

SQUARIC ACID AS A VERSATILE COMPOUND IN THE DESIGN OF
MOLECULAR SOLIDS





Von der Fakultät für Mathematik, Informatik und Naturwissenschaften der RWTH Aachen
University zur Erlangung des akademischen Grades einer Doktorin der
Naturwissenschaften genehmigte Dissertation




vorgelegt von


M. Sc. Mihaela Diana ŞERB, geb. DURIGU


aus Cimpulung Muscel, Romania


Berichter: Professor Dr. rer. nat. Ulli Englert
Professor Dr. rer. nat. Heiko Lueken



Tag der mündlichen Prüfung: 19.12.2008

Diese Dissertation ist auf den Internetseiten der Hochschulbibliothek online verfügbar. The work reported here has been carried out at the Department of Inorganic
Chemistry, University Politehnica of Bucharest under the supervision of Prof. Dr.
Cornelia Guran between November 2003 - September 2007 and at the Institute of
Inorganic Chemistry, RWTH Aachen University under the supervision of Prof. Dr. Ulli
Englert between October 2007 - October 2008.

Part of this work has been published:

1. M.-D. Serb, B. Calmuschi-Cula, F. Dumitru, C. Guran and U. Englert
Synthesis and structural characterization of tris[4-(2-pyridylmethyleneamino)-
phenol]manganese(II)bis(perchlorate)
U.P.B. Sci. Bull., Series B, Vol. 70, No. 4, 2008, 45-51.
2. M.-D. Serb, B. Calmuschi-Cula, F. Dumitru, U. Englert and C. Guran
Tris(2-pyridinecarboxaldehyde(p-hydroxyphenylimine))iron(II)diperchlorate complex
Acta Cryst., 2008, E64, m212- m213.
3. M.-D. Serb, B. Calmuschi-Cula, F. Dumitru, U. Englert and C. Guran
Catena-Poly{[bis(acetonitrile)(1,10-phenanthroline-N,N’)copper(II)]-µ-perchlorato-
O,O}(perchlorate)
Acta Cryst., 2007, E63, 1484-1486.
4. M.-D. Serb, B. Calmuschi-Cula, T. Dols, F. Dumitru, U. Englert and C. Guran
Bis(1,10 phenanthroline)acetonitrilecopper(II)diperchlorates complex
Acta Cryst., 2007, E63, 1292-1293.

or presented in international conferences:

1. 5th European Charge Density Meeting, Como, June 06-11, 2008, poster
presentation
2. British Crystallography Association Annual Meeting, York, April 08-10, 2008, poster
presentation
3. Proceedings of Chemistry and Chemical Engineering, RICCCE 14, Bucharest,
September, 2005, oral presentation
4. Junior Euromat, Lausanne, Switzerland, September 2004, poster presentation
th5. 4 International Conference of the Chemical Societies of the South-East European
Countries on Chemical Sciences in Changing Times: Visions, Challenges and
solutions, Belgrade, July, 2004, poster presentation
1. Introduction ..............................................................................................................4
1.1. General Remarks ..............................................................................................4
1.2. Squaric acid.......................................................................................................5
1.3. Aim ....................................................................................................................6
2. Hydrogen-bonded systems generated by the squaric acid ......................................8
2.1. Characteristics of graphs.................................................................................10
242.1.1 Graph−set definitions ..............................................................................10
2.1.2 Rules applied in graphs .............................................................................11
2.2. Supramolecular hydrogen−bonds in biguanidinium squarates ........................11
2.2.1. Crystal structure of N, N−dimethylbiguanide squarates............................12
2.2.1.1. N, N−dimethylbiguanidinium−bis(hydrogensquarate),
(C H N )(C HO ) , 1a ....................................................................................12 4 13 5 4 4 2
2.2.1.2. N, N−dimethylbiguanidinium squarate dihydrate,
(C H N )(C O )(OH ) , 1b..............................................................................19 4 13 5 4 4 2 2
2.2.1.3. N, N−dimethylbiguanidinium−squarate hydrate, (C H N )(C O )(OH ), 4 13 5 4 4 2
1c ....................................................................................................................24
2.2.1.4. Monohydrogen−(N, N−dimethylbiguanidinium)−hemisquarate hydrate,
(C H N )(C O ) (OH ) , 1d...........................................................................30 4 12 5 4 4 0.5 2
2.2.1.5. Results and discussion.......................................................................36
2.2.2. Crystal structures of Phenylbiguanide squarates......................................39
2.2.2.1.
(monohydrogen−N−phenylbiguanidinium)−(N−phenylbiguanidinium)−(hydroge
nsquarate)−squarate solvate, (C H N )(C H N )(C HO )(C O )(C H O) , 2a8 12 5 8 13 5 4 4 4 4 2 6 0.5
........................................................................................................................39
2.2.2.2. Bis−(monohydrogen−N−phenylbiguanidinium)−squarate,
(C H N ) (C O ), 2b.......................................................................................46 8 12 5 2 4 4
2.2.2.3. Results and discussion.......................................................................51
2.2.3. Crystal structure of ortho−tolylbiguanide squarates..................................53
2.2.3.1 ortho-tolylbiguanidinium squarate, (C H N )(C O )(OH ), 3a.............53 9 15 5 4 4 2
2.2.3.2. (Monohydrogen−o−tolylbiguanidinium)−(o−tolylbiguanidinium)
−(hydrogensquarate)−squarate, (C H N )(C H N )(C HO )(C O ), 3b.........60 9 14 5 9 15 5 4 4 4 4
2.2.3.3. o−tolylbiguanidinium−squarate hydrate, (C H N )(C O )(OH ), 3c ...67 9 15 5 4 4 2
2.2.3.4. Monohydrogen−(o−tolylbiguanidinium)−hemisquarate,
(C H N )(C O ) , 3d .....................................................................................76 9 14 5 4 4 0.5
2.2.3.5. Results and discussion.......................................................................81
2.2.4. Conclusions ..............................................................................................83
3. Design of polynuclear complexes with squaric acid as ligand ............................88
3.1. Building-blocks strategy in the design of dinuclear squarate complexes.........89
3.1.1. The design of the phenanthroline based-building blocks ..........................89
3.1.1.1 Diaqua−bis(1,10−phenanthroline)manganese(II)bis(perchlorate)
benzene solvate, [Mn(OH ) (phen) ](ClO ) ·C H (1-Mn) ..............................89 2 2 2 4 2 6 6
3.1.1.2
2Catena−Poly[[[bis(acetonitrile)(1,10−phenanthroline−k N,N’)copper(II)]−m−per
2chlorato−k O:O’] perchlorate], {[Cu(CH CN) (phen)(ClO )](ClO )} , (2-Cu)....92 3 2 4 4 n
3.1.1.3. Diaqua−(1,10−phenanthroline)bis(perchlorate)copper(II),
[Cu(OH ) (phen)(ClO ) ], (3-Cu)......................................................................94 2 2 4 2
3.1.1.4 (Acetonitrile)bis(1,10−phenanthroline)copper(II)-bis(perchlorate),
[Cu(phen) (CH CN)](ClO ) , (4-Cu).................................................................97 2 3 4 2
533.1.2. Design of (2−pyridylmethyleneamino)−phenol -building blocks...............99 3.1.2.1 Tris[4−(2−pyridylmethyleneamino)−phenol]iron(II)bis(perchlorate),
[Fe(C H N O) ](ClO ) , (5-Fe) ......................................................................99 12 10 2 3 4 2
3.1.2.2.
Tris[4−(2−pyridylmethyleneamino)−phenol]manganese(II)bis(perchlorate),
[Mn(C H N O) ](ClO ) , (6-Mn)..................................................................102 12 10 2 3 4 2
3.1.3. Design of dinuclear squarate complex,...................................................105
dicopper(II)-(µ−1,2−squarato)-tetra(1,10-phenanthroline)-bisperchlorate-solvate,
{[Cu (phen) (C O )](ClO ) } solvate, (7-Cu) ....................................................105 2 4 4 4 4 2 2
3.2. Design of coordination complexes that self-assemble into two-dimensional
supramolecular networks .....................................................................................108
3.2.1. catena(m -Squarato-O,O’)-(bis(dimethylsulfoxide-O)-diaqua-M(II)), 2
II II[M (C O )(C H SO) (OH ) ] , where M = Co, Mn, ‘Co+Mn’, (8-Co, 9-Mn, 10-4 4 2 6 2 2 2 n
Co+Mn).............................................................................................................108
2 1 33.2.2. Catena-poly[[diaqua-(dimethylsulfoxide)−m −squarato−k O :O ]-copper(II), 2
II[Cu (C O )(C H SO)(OH ) ] , (11-Cu) ..............................................................112 4 4 2 6 2 2 n
3.3. Conclusions...................................................................................................116
4. Ag(I)−squarate coordination polymers .................................................................121
4.1. Silver squarate, [(Ag C O ) ] , (12-Ag)........................................................122 2 4 4 0.5 n
2 1 34.2. catena−Poly−(disilver(I)−m−hydrogensquarato−k O :O −bis(pyrazinyl−N,N’)
(hydrogensquarate), {[Ag (pyz) (C HO )](C HO )} , (13-Ag)................................123 2 2 4 4 4 4 n
4.3. Conclusions...................................................................................................128
5. Experimental Section...........................................................................................129
5.1