Solvatochromic and ionochromic effects of iron(II)bis-(1, 10-phenanthroline)dicyano: A Theoretical Study

Ivelina Georgieva; Ad́elia J.A. Aquino; Natasha Trendafilova; Paulo S. Santos; Hans Lischka

doi:10.1021/ic9020299

Solvatochromic and ionochromic effects of iron(II)bis-(1, 10-phenanthroline)dicyano: A Theoretical Study

Ivelina Georgieva, Ad́elia J.A. Aquino, Natasha Trendafilova, Paulo S. Santos, Hans Lischka

Chemistry and Biochemistry

Research output: Contribution to journal › Article › peer-review

22 Scopus citations

Abstract

Solvatochromic and ionochromic effects of the iron(II)bis(1, 10-phenanthroline)dicyano (Fe(phen)₂(CN)₂) complex were investigated by means of combined DFT/TDDFT calculations using the PBE and B3LYP functionals. Extended solvation models of Fe(phen)₂(CN)₂ in acetonitrile and aqueous solution, as well as including interaction with Mg²⁺, were constructed. The calculated vertical excitation energies reproduce well the observed solvatochromism in acetonitrile and aqueous solutions, the ionochromism in acetonitrile in the presence of Mg²⁺, and the absence of ionochromic effect in aqueous solution. The vertical excitation energies and the nature of the transitions were reliably predicted after inclusion of geometry relaxation upon aqueous micro-and global solvation and solvent polarization effect in the TDDFT calculations. The two intense UV-vis absorption bands occurring for all systems studied are interpreted as transitions from a hybrid Fe^II(d)/cyano N(p) orbital to a phenanthroline π ^* orbital rather than a pure metal-to-ligand-charge transfer (MLCT). The solvatochromic and ionochromic blue band shifts of Fe(phen)₂(CN)₂ were explained with preferential stabilization of the highest occupied FeII(d)/cyano N(p) orbitals as a result of specific interactions with water solvent molecules or Mg ²⁺ ions in solution. Such interactions occur through the CN ^- groups in the complex, and they have a decisive role for the observed blue shifts of UV-vis absorption bands.

Original language	English
Pages (from-to)	1634-1646
Number of pages	13
Journal	Inorganic Chemistry
Volume	49
Issue number	4
DOIs	https://doi.org/10.1021/ic9020299
State	Published - Feb 15 2010

Access to Document

10.1021/ic9020299

Cite this

@article{357bb90a1d3a4665b7b6db445213b07c,

title = "Solvatochromic and ionochromic effects of iron(II)bis-(1, 10-phenanthroline)dicyano: A Theoretical Study",

abstract = "Solvatochromic and ionochromic effects of the iron(II)bis(1, 10-phenanthroline)dicyano (Fe(phen)2(CN)2) complex were investigated by means of combined DFT/TDDFT calculations using the PBE and B3LYP functionals. Extended solvation models of Fe(phen)2(CN)2 in acetonitrile and aqueous solution, as well as including interaction with Mg2+, were constructed. The calculated vertical excitation energies reproduce well the observed solvatochromism in acetonitrile and aqueous solutions, the ionochromism in acetonitrile in the presence of Mg2+, and the absence of ionochromic effect in aqueous solution. The vertical excitation energies and the nature of the transitions were reliably predicted after inclusion of geometry relaxation upon aqueous micro-and global solvation and solvent polarization effect in the TDDFT calculations. The two intense UV-vis absorption bands occurring for all systems studied are interpreted as transitions from a hybrid FeII(d)/cyano N(p) orbital to a phenanthroline π * orbital rather than a pure metal-to-ligand-charge transfer (MLCT). The solvatochromic and ionochromic blue band shifts of Fe(phen)2(CN)2 were explained with preferential stabilization of the highest occupied FeII(d)/cyano N(p) orbitals as a result of specific interactions with water solvent molecules or Mg 2+ ions in solution. Such interactions occur through the CN - groups in the complex, and they have a decisive role for the observed blue shifts of UV-vis absorption bands.",

author = "Ivelina Georgieva and Aquino, {A{\'d}elia J.A.} and Natasha Trendafilova and Santos, {Paulo S.} and Hans Lischka",

year = "2010",

month = feb,

day = "15",

doi = "10.1021/ic9020299",

language = "English",

volume = "49",

pages = "1634--1646",

journal = "Inorganic Chemistry",

issn = "0020-1669",

publisher = "American Chemical Society",

number = "4",

}

TY - JOUR

T1 - Solvatochromic and ionochromic effects of iron(II)bis-(1, 10-phenanthroline)dicyano

T2 - A Theoretical Study

AU - Georgieva, Ivelina

AU - Aquino, Ad́elia J.A.

AU - Trendafilova, Natasha

AU - Santos, Paulo S.

AU - Lischka, Hans

PY - 2010/2/15

Y1 - 2010/2/15

N2 - Solvatochromic and ionochromic effects of the iron(II)bis(1, 10-phenanthroline)dicyano (Fe(phen)2(CN)2) complex were investigated by means of combined DFT/TDDFT calculations using the PBE and B3LYP functionals. Extended solvation models of Fe(phen)2(CN)2 in acetonitrile and aqueous solution, as well as including interaction with Mg2+, were constructed. The calculated vertical excitation energies reproduce well the observed solvatochromism in acetonitrile and aqueous solutions, the ionochromism in acetonitrile in the presence of Mg2+, and the absence of ionochromic effect in aqueous solution. The vertical excitation energies and the nature of the transitions were reliably predicted after inclusion of geometry relaxation upon aqueous micro-and global solvation and solvent polarization effect in the TDDFT calculations. The two intense UV-vis absorption bands occurring for all systems studied are interpreted as transitions from a hybrid FeII(d)/cyano N(p) orbital to a phenanthroline π * orbital rather than a pure metal-to-ligand-charge transfer (MLCT). The solvatochromic and ionochromic blue band shifts of Fe(phen)2(CN)2 were explained with preferential stabilization of the highest occupied FeII(d)/cyano N(p) orbitals as a result of specific interactions with water solvent molecules or Mg 2+ ions in solution. Such interactions occur through the CN - groups in the complex, and they have a decisive role for the observed blue shifts of UV-vis absorption bands.

AB - Solvatochromic and ionochromic effects of the iron(II)bis(1, 10-phenanthroline)dicyano (Fe(phen)2(CN)2) complex were investigated by means of combined DFT/TDDFT calculations using the PBE and B3LYP functionals. Extended solvation models of Fe(phen)2(CN)2 in acetonitrile and aqueous solution, as well as including interaction with Mg2+, were constructed. The calculated vertical excitation energies reproduce well the observed solvatochromism in acetonitrile and aqueous solutions, the ionochromism in acetonitrile in the presence of Mg2+, and the absence of ionochromic effect in aqueous solution. The vertical excitation energies and the nature of the transitions were reliably predicted after inclusion of geometry relaxation upon aqueous micro-and global solvation and solvent polarization effect in the TDDFT calculations. The two intense UV-vis absorption bands occurring for all systems studied are interpreted as transitions from a hybrid FeII(d)/cyano N(p) orbital to a phenanthroline π * orbital rather than a pure metal-to-ligand-charge transfer (MLCT). The solvatochromic and ionochromic blue band shifts of Fe(phen)2(CN)2 were explained with preferential stabilization of the highest occupied FeII(d)/cyano N(p) orbitals as a result of specific interactions with water solvent molecules or Mg 2+ ions in solution. Such interactions occur through the CN - groups in the complex, and they have a decisive role for the observed blue shifts of UV-vis absorption bands.

UR - http://www.scopus.com/inward/record.url?scp=77249098812&partnerID=8YFLogxK

U2 - 10.1021/ic9020299

DO - 10.1021/ic9020299

M3 - Article

C2 - 20055424

AN - SCOPUS:77249098812

VL - 49

SP - 1634

EP - 1646

JO - Inorganic Chemistry

JF - Inorganic Chemistry

SN - 0020-1669

IS - 4

ER -

Solvatochromic and ionochromic effects of iron(II)bis-(1, 10-phenanthroline)dicyano: A Theoretical Study

Abstract

Access to Document

Other files and links

Fingerprint

Cite this