Ligand Effects toward the Modulation of Magnetic Anisotropy and Design of Magnetic Systems with Desired Anisotropy Characteristics

被引：30

作者：

Goswami, Tamal ^{[1
]}

Misra, Anirban ^{[1
]}

机构：

[1] Univ N Bengal, Dept Chem, Darjeeling 734013, W Bengal, India

来源：

JOURNAL OF PHYSICAL CHEMISTRY A | 2012年 / 116卷 / 21期

关键词：

SINGLE-MOLECULE MAGNETS; ELECTRON-PARAMAGNETIC-RESONANCE; ZERO-FIELD SPLITTINGS; 2ND-ORDER OPTICAL NONLINEARITIES; TRANSITION-METAL-COMPLEXES; DENSITY-FUNCTIONAL THEORY; GAUSSIAN-BASIS SETS; HIGH-SPIN MOLECULES; CHAIN MAGNET; GROUND-STATE;

D O I：

10.1021/jp3006603

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：

Magnetic anisotropy of a set of octahedral Cr(III) complexes is studied theoretically. The magnetic anisotropy is quantified in terms of zero-field splitting (ZFS) parameter D, which appeared sensitive toward ligand substitution. The increased pi-donation capacity of the ligand enhances the magnetic anisotropy of the complexes. The axial pi-donor ligand of a complex is found to produce an easy-plane type (D > 0) magnetic anisotropy, while the replacement of the axial ligands with pi a-acceptors entails the inversion of magnetic anisotropy into the easy-axis type (D < 0). This observation enables one to fabricate a single molecule magnet for which easy-axis type magnetic anisotropy is an indispensable criterion. The equatorial ligands are also found to play a role in tuning the magnetic anisotropy. The magnetic anisotropy property is also correlated with the nonlinear optical (NLO) response. The value of the first hyperpolarizability varies proportionately with the magnitude of the ZFS parameter. Finally, it has also been shown that a rational design of simple octahedral complexes with desired anisotropy characteristics is possible through the proper ligand selection.

引用

页码：5207 / 5215

页数：9

共 104 条

[21]

2-U

[22] Slow Relaxation of the Magnetization in Non-Linear Optical Active Layered Mixed Metal Oxalate Chains [J].

Cariati, Elena ;

Ugo, Renato ;

Santoro, Giuseppe ;

Tordin, Elisa ;

Sorace, Lorenzo ;

Caneschi, Andrea ;

Sironi, Angelo ;

Macchi, Piero ;

Casati, Nicola .

INORGANIC CHEMISTRY, 2010, 49 (23) :10894-10901

[23] PI-INTERACTIONS IN METALLOPORPHYRINS AND HEMEPROTEINS [J].

CAUGHEY, WS ;

EBERSPAECHER, H ;

FUCHSMAN, WH ;

MCCOY, S .

ANNALS OF THE NEW YORK ACADEMY OF SCIENCES, 1969, 153 (A3) :722-+

[24] Evidence for single-chain magnet behavior in a MnIII-NiII chain designed with high spin magnetic units:: A route to high temperature metastable magnets [J].

Clérac, R ;

Miyasaka, H ;

Yamashita, M ;

Coulon, C .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2002, 124 (43) :12837-12844

[25] Magnetic and optical studies on an S=6 ground-state cluster [Cr12O9(OH)3(O2CCMe3)15]:: Determination of, and the relationship between, single-ion and cluster spin Hamiltonian parameters [J].

Collison, D ;

Murrie, M ;

Oganesyan, VS ;

Piligkos, S ;

Poolton, NRJ ;

Rajaraman, G ;

Smith, GM ;

Thomson, AJ ;

Timko, GA ;

Wernsdorfer, W ;

Winpenny, REP ;

McInnes, EJL .

INORGANIC CHEMISTRY, 2003, 42 (17) :5293-5303

[26]

de Andrade A.V.M., 1997, MOL ENG, V7, P293, DOI DOI 10.1023/A:1008227001656

[27] Mossbauer and electron paramagnetic resonance studies of chloroperoxidase following mechanism-based inactivation with allylbenzene [J].

Debrunner, PG ;

Dexter, AF ;

Schulz, CE ;

Xia, YM ;

Hager, LP .

PROCEEDINGS OF THE NATIONAL ACADEMY OF SCIENCES OF THE UNITED STATES OF AMERICA, 1996, 93 (23) :12791-12798

[28] Electronic structure of four-coordinate C3v nickel(II) scorpionate complexes:: Investigation by high-frequency and -field electron paramagnetic resonance and electronic absorption spectroscopies [J].

Desrochers, Patrick J. ;

Telser, Joshua ;

Zvyagin, S. A. ;

Ozarowski, Andrew ;

Krzystek, J. ;

Vicic, David A. .

INORGANIC CHEMISTRY, 2006, 45 (22) :8930-8941

[29] Cyclometallated iridium(III) complexes with substituted 1,10-phenanthrolines: a new class of highly active organometallic second order NLO-phores with excellent transparency with respect to second harmonic emission [J].

Dragonetti, Claudia ;

Righetto, Stefania ;

Roberto, Dominique ;

Ugo, Renato ;

Valore, Adriana ;

Fantacci, Simona ;

Sgamellotti, Antonio ;

De Angelis, Filippo .

CHEMICAL COMMUNICATIONS, 2007, (40) :4116-4118

[30] Origin of the zero-field splitting in mononuclear octahedral dihalide MnII complexes:: An investigation by multifrequency high-field electron paramagnetic resonance and density functional theory [J].

Duboc, Carole ;

Phoeung, Thida ;

Zein, Samir ;

Pecaut, Jacques ;

Collomb, Marie-Noelle ;

Neese, Frank .

INORGANIC CHEMISTRY, 2007, 46 (12) :4905-4916

← 1 2 3 4 5 6 7 8 9 10 →