Insights into bonding interactions and excitation energies of 3d–4f mixed lanthanide transition metal macrocyclic complexes

2016 ◽  
Vol 18 (48) ◽  
pp. 33218-33225 ◽  
Author(s):  
Walter A. Rabanal-León ◽  
Juliana A. Murillo-López ◽  
Ramiro Arratia-Pérez
Keyword(s):  
Transition Metal ◽  
Transition Metals ◽  
Coordination Compounds ◽  
Spectroscopic Properties ◽  
Macrocyclic Complexes ◽  
Excitation Energies

This work provides insights into the metal/macrocyclic (host–guest) interaction and spectroscopic properties of the macrocyclic coordination compounds containing both lanthanide and transition metals inside their framework.

scholarly journals Intermolecular interaction energies in transition metal coordination compounds

CrystEngComm ◽  
2015 ◽  
Vol 17 (48) ◽  
pp. 9300-9310 ◽  
Author(s):  
Andrew G. P. Maloney ◽  
Peter A. Wood ◽  
Simon Parsons
Keyword(s):  
Transition Metal ◽  
Transition Metals ◽  
Crystal Structures ◽  
Intermolecular Interaction ◽  
Coordination Compounds ◽  
Metal Coordination ◽  
Interaction Energies

The PIXEL method has been parameterised and validated for transition metals, extending its applicability from ~40% to ~85% of all published crystal structures.

scholarly journals The reactions of α-amino acids and α-amino acid esters with high valent transition metal halides: synthesis of coordination complexes, activation processes and stabilization of α-ammonium acylchloride cations

RSC Advances ◽  
2017 ◽  
Vol 7 (17) ◽  
pp. 10158-10174 ◽  
Author(s):  
Lorenzo Biancalana ◽  
Marco Bortoluzzi ◽  
Eleonora Ferretti ◽  
Mohammad Hayatifar ◽  
Fabio Marchetti ◽  
...  
Keyword(s):  
Amino Acids ◽  
Amino Acid ◽  
Transition Metal ◽  
Transition Metals ◽  
Coordination Compounds ◽  
Coordination Complexes ◽  
Amino Acid Esters ◽  
Metal Halides ◽  
High Valent ◽  
Acid Esters

We describe the synthesis of rare coordination compounds of early transition metals with α-amino acids and α-amino acid esters, the unusual C–C dimerization ofl-proline, and the stabilization of reactive α-ammonium acylchloride cations.

Transition metal coordination complexes of chrysazin

CrystEngComm ◽  
2016 ◽  
Vol 18 (27) ◽  
pp. 5121-5129 ◽  
Author(s):  
Patrick J. Beldon ◽  
Sebastian Henke ◽  
Bartomeu Monserrat ◽  
Satoshi Tominaka ◽  
Norbert Stock ◽  
...  
Keyword(s):  
Transition Metal ◽  
Transition Metals ◽  
Single Crystal ◽  
Coordination Compounds ◽  
Coordination Complexes ◽  
Metal Coordination ◽  
X Ray Diffraction ◽  
X Ray

Eleven novel coordination compounds, composed of chrysazin (1,8-dihydroxyanthraquinone) and different first-row transition metals (Fe, Co, Ni, Cu), were synthesised and the structures determined by single-crystal X-ray diffraction.

Synthesis, Crystal Structures, and Thermal and Spectroscopic Properties of Thiocyanato Coordination Compounds with 3-Acetylpyridine as a Ligand

2014 ◽  
Vol 69 (11-12) ◽  
pp. 1419-1428
Author(s):  
Julia Werner ◽  
Inke Jeß ◽  
Christian Näther
Keyword(s):  
Transition Metal ◽  
Crystal Structures ◽  
Coordination Polymers ◽  
Coordination Compounds ◽  
Spectroscopic Properties ◽  
Second Step ◽  
Crystalline Phases ◽  
Thermogravimetric Investigations ◽  
New Compounds ◽  
Ir Spectroscopic

Abstract The reaction of transition metal thiocyanates with 3-acetylpyridine (3-Acpy) leads to the formation of compounds of compositions M(NCS)2(3-Acpy)4 (M1; M = Mn, Fe, Ni) and M(NCS)2(3- Acpy)2(H2O)2 (M2; M = Mn, Fe, Ni). Thermogravimetric investigations show that in the first step some of these compounds transform into the new coordination polymers M(NCS)2(3-Acpy)2 (M3 with M = Mn, Fe and Ni), that decompose into the new compounds M(NCS)2(3-Acpy) (M4 with M = Mn and Ni) in the second step. Unfortunately, the powder patterns of compounds M3 and M4 cannot be indexed, and there are strong indications that these compounds are contaminated with a small amount of the precursor or unknown crystalline phases. IR spectroscopic investigations indicate that in compounds M3 the metal cations are linked by μ-1,3-bridging thiocyanato anions into 1D or 2D coordination polymers that are further linked by the 3-Acpy ligands in compounds M4.

Uber Organometall-Verbindungen von Stickstoff-Systemen IV

1970 ◽  
Vol 25 (12) ◽  
pp. 1358-1363 ◽  
Author(s):  
Dieter Tille
Keyword(s):  
Transition Metal ◽  
Coordination Compounds ◽  
Spectroscopic Properties ◽  
Metal Halides ◽  
Anaerobic Conditions ◽  
Derivatives Of ◽  
Nitrogen Bond

As known from various biological important macrocycles (porphyrines, corrines) the single heterocycle C4H5N is able to form pyrrolyl compounds with a transition metal-to-nitrogen bond. These can be synthesized from metal halides and LiPyrr in ether or THF under anaerobic conditions. Binary and coordination compounds as well as Cp-derivatives of both Ti and Ni, their chemical, magnetic, IR- and PMR-spectroscopic properties are described to confirm the structures

scholarly journals A Theoretical Study of the Occupied and Unoccupied Electronic Structure of High- and Intermediate-Spin Transition Metal Phthalocyaninato (Pc) Complexes: VPc, CrPc, MnPc, and FePc

Nanomaterials ◽  
2020 ◽  
Vol 11 (1) ◽  
pp. 54
Author(s):  
Silvia Carlotto ◽  
Mauro Sambi ◽  
Francesco Sedona ◽  
Andrea Vittadini ◽  
Maurizio Casarin
Keyword(s):  
Electronic Structure ◽  
Transition Metal ◽  
Density Functional ◽  
Spin Transition ◽  
Electronic States ◽  
Spectroscopic Properties ◽  
Open Shell ◽  
Excitation Energies ◽  
Intermediate Spin ◽  
Charge Transfer Transitions

The structural, electronic, and spectroscopic properties of high- and intermediate-spin transition metal phthalocyaninato complexes (MPc; M = V, Cr, Mn and Fe) have been theoretically investigated to look into the origin, symmetry and strength of the M–Pc bonding. DFT calculations coupled to the Ziegler’s extended transition state method and to an advanced charge density and bond order analysis allowed us to assess that the M–Pc bonding is dominated by σ interactions, with FePc having the strongest and most covalent M–Pc bond. According to experimental evidence, the lightest MPcs (VPc and CrPc) have a high-spin ground state (GS), while the MnPc and FePc GS spin is intermediate. Insights into the MPc unoccupied electronic structure have been gained by modelling M L2,3-edges X-ray absorption spectroscopy data from the literature through the exploitation of the current Density Functional Theory variant of the Restricted Open-Shell Configuration Interaction Singles (DFT/ROCIS) method. Besides the overall agreement between theory and experiment, the DFT/ROCIS results indicate that spectral features lying at the lowest excitation energies (EEs) are systematically generated by electronic states having the same GS spin multiplicity and involving M-based single electronic excitations; just as systematically, the L3-edge higher EE region of all the MPcs herein considered includes electronic states generated by metal-to-ligand-charge-transfer transitions involving the lowest-lying π* orbital (7eg) of the phthalocyaninato ligand.

Intercalation of First Row Transition Metals inside Covalent-Organic Frameworks (COF): a Strategy to Fine Tune the Electronic Properties of Porous Crystalline Materials

2018 ◽  
Author(s):  
Srimanta Pakhira ◽  
Jose Mendoza-Cortes
Keyword(s):  
Transition Metal ◽  
Transition Metals ◽  
Electronic Properties ◽  
High Surface ◽  
Electronic Devices ◽  
High Surface Area ◽  
Main Role ◽  
Covalent Organic Frameworks ◽  
Porous Network ◽  
Crystalline Materials

<div>Covalent organic frameworks (COFs) have emerged as an important class of nano-porous crystalline materials with many potential applications. They are intriguing platforms for the design of porous skeletons with special functionality at the molecular level. However, despite their extraordinary properties, it is difficult to control their electronic properties, thus hindering the potential implementation in electronic devices. A new form of nanoporous material, COFs intercalated with first row transition metal is proposed to address this fundamental drawback - the lack of electronic tunability. Using first-principles calculations, we have designed 31 new COF materials <i>in-silico</i> by intercalating all of the first row transition metals (TMs) with boroxine-linked and triazine-linked COFs: COF-TM-x (where TM=Sc-Zn and x=3-5). This is a significant addition considering that only 187 experimentally COFs structures has been reported and characterized so far. We have investigated their structure and electronic properties. Specifically, we predict that COF's band gap and density of states (DOSs) can be controlled by intercalating first row transition metal atoms (TM: Sc - Zn) and fine tuned by the concentration of TMs. We also found that the $d$-subshell electron density of the TMs plays the main role in determining the electronic properties of the COFs. Thus intercalated-COFs provide a new strategy to control the electronic properties of materials within a porous network. This work opens up new avenues for the design of TM-intercalated materials with promising future applications in nanoporous electronic devices, where a high surface area coupled with fine-tuned electronic properties are desired.</div>

Bond-length distributions for ions bonded to oxygen: Metalloids and post-transition metals

2017 ◽  
Author(s):  
Olivier Charles Gagné ◽  
Frank Christopher Hawthorne
Keyword(s):  
Transition Metal ◽  
Transition Metals ◽  
Metal Ions ◽  
Bond Length ◽  
Lone Pair ◽  
Transition Metal Ions ◽  
Oxygen Lone Pair

Bond-length distributions are examined for thirty-three configurations of the metalloid ions and fifty-six configurations of the post-transition-metal ions bonded to oxygen. Lone-pair stereoactivity is discussed.

Bond-length distributions for ions bonded to oxygen: Metalloids and post-transition metals

2017 ◽  
Author(s):  
Olivier Charles Gagné ◽  
Frank Christopher Hawthorne
Keyword(s):  
Transition Metal ◽  
Transition Metals ◽  
Metal Ions ◽  
Bond Length ◽  
Lone Pair ◽  
Transition Metal Ions ◽  
Oxygen Lone Pair

Bond-length distributions are examined for thirty-three configurations of the metalloid ions and fifty-six configurations of the post-transition-metal ions bonded to oxygen. Lone-pair stereoactivity is discussed.

Electronic properties of quasi two-dimensional transition metals chalcogenides with low-dimensional magnetism

Doklady BGUIR ◽  
2020 ◽  
Vol 18 (7) ◽  
pp. 87-95
Author(s):  
M. S. Baranava ◽  
P. A. Praskurava
Keyword(s):  
Transition Metal ◽  
Transition Metals ◽  
Exchange Interaction ◽  
Electronic Properties ◽  
Metal Atom ◽  
Transition Metal Atom ◽  
Two Dimensional ◽  
Transition Metal Atoms ◽  
Ground Magnetic ◽  
Low Dimensional

The search for fundamental physical laws which lead to stable high-temperature ferromagnetism is an urgent task. In addition to the already synthesized two-dimensional materials, there remains a wide list of possible structures, the stability of which is predicted theoretically. The article suggests the results of studying the electronic properties of MAX3 (M = Cr, Fe, A = Ge, Si, X = S, Se, Te) transition metals based compounds with nanostructured magnetism. The research was carried out using quantum mechanical simulation in specialized VASP software and calculations within the Heisenberg model. The ground magnetic states of twodimensional MAX3 and the corresponding energy band structures are determined. We found that among the systems under study, CrGeTe3 is a semiconductor nanosized ferromagnet. In addition, one is a semiconductor with a bandgap of 0.35 eV. Other materials are antiferromagnetic. The magnetic moment in MAX3 is localized on the transition metal atoms: in particular, the main one on the d-orbital of the transition metal atom (and only a small part on the p-orbital of the chalcogen). For CrGeTe3, the exchange interaction integral is calculated. The mechanisms of the formation of magnetic order was established. According to the obtained exchange interaction integrals, a strong ferromagnetic order is formed in the semiconductor plane. The distribution of the projection density of electronic states indicates hybridization between the d-orbital of the transition metal atom and the p-orbital of the chalcogen. The study revealed that the exchange interaction by the mechanism of superexchange is more probabilistic.

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