Quantifying aromaticity at the molecular and supramolecular limits: Comparing homonuclear, heteronuclear, and H-bonded systems

被引:51
作者
Rehaman, A
Datta, A
Mallajosyula, SS
Pati, SK
机构
[1] Jawaharlal Nehru Ctr Adv Sci Res, Theoret Sci Unit, Bangalore 560064, Karnataka, India
[2] Jawaharlal Nehru Ctr Adv Sci Res, Chem & Phys Mat Unit, Bangalore 560064, Karnataka, India
关键词
D O I
10.1021/ct0501598
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
The aromatic/antiaromatic characteristics of B-N and P-N analogues of benzene and cyclobutadiene have been studied using quantum chemical methods. We use established parameters such as nucleus-independent chemical shifts, charge density at the ring critical point, and stabilization energies to quantify the nature of interactions in these molecular systems. B3N3H6 and N3P3F6 resemble benzene in being aromatic, albeit to a lesser extent, while B2N2H4 and N2P2F4 are found to be aromatic, opposite to that for cyclobutadiene. A sigma-pi separation analysis has been performed to critically examine the contributions from the pi electrons compared to that from the sigma backbone. The structural aspects in the weak interaction limits such as the H-bonded cyclic trimers of HX (X = F, Cl, and Br) have also been investigated. Even in such weak interaction limits, these cyclic systems are found to be substantially stable. These H-bonded systems exhibit nonlocal polarizations across the full-perimeter of the ring that lead to aromaticity. We propose the term '' H-bonded aromaticity '' for such closed-loop weakly delocalized systems. This new formalism of aromaticity has the potential to explain structures and properties in supramolecular systems.
引用
收藏
页码:30 / 36
页数:7
相关论文
共 62 条
[1]   Synthesis of a Mobius aromatic hydrocarbon [J].
Ajami, D ;
Oeckler, O ;
Simon, A ;
Herges, R .
NATURE, 2003, 426 (6968) :819-821
[2]   RECENT ADVANCES IN PHOSPHAZENE (PHOSPHONITRILIC) CHEMISTRY [J].
ALLCOCK, HR .
CHEMICAL REVIEWS, 1972, 72 (04) :315-&
[3]   SYNTHESIS AND STRUCTURE OF THE 1ST CYCLODIPHOSPHAZENE - DIMERIZATION OF A PHOSPHONITRILE GREATER-THAN-P=N [J].
BACEIREDO, A ;
BERTRAND, G ;
MAJORAL, JP ;
SICARD, G ;
JAUD, J ;
GALY, J .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1984, 106 (20) :6088-6089
[4]  
Bader R.F. W., 1995, Atoms in Molecules: A Quantum Theory
[5]  
BECKE AD, 1988, PHYS REV A, V37, P785, DOI DOI 10.1103/PHYS.REV.B.37-785
[6]   PATTERNS IN HYDROGEN BONDING - FUNCTIONALITY AND GRAPH SET ANALYSIS IN CRYSTALS [J].
BERNSTEIN, J ;
DAVIS, RE ;
SHIMONI, L ;
CHANG, NL .
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 1995, 34 (15) :1555-1573
[7]   EVIDENCE FOR RESONANCE-ASSISTED HYDROGEN-BONDING .2. INTERCORRELATION BETWEEN CRYSTAL-STRUCTURE AND SPECTROSCOPIC PARAMETERS IN 8 INTRAMOLECULARLY HYDROGEN-BONDED 1,3-DIARYL-1,3-PROPANEDIONE ENOLS [J].
BERTOLASI, V ;
GILLI, P ;
FERRETTI, V ;
GILLI, G .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1991, 113 (13) :4917-4925
[8]   ELECTRONIC AND STRUCTURAL-PROPERTIES OF BORAZINE AND RELATED MOLECULES [J].
BOYD, RJ ;
CHOI, SC ;
HALE, CC .
CHEMICAL PHYSICS LETTERS, 1984, 112 (02) :136-141
[9]   CALCULATION OF SMALL MOLECULAR INTERACTIONS BY DIFFERENCES OF SEPARATE TOTAL ENERGIES - SOME PROCEDURES WITH REDUCED ERRORS [J].
BOYS, SF ;
BERNARDI, F .
MOLECULAR PHYSICS, 1970, 19 (04) :553-&
[10]  
*CAMBR CRYST DAT C, 2004, CONQ VERS 1 7 CAMBR