The title metal-organic polymer, catena-poly[[(5,5'-dimethyl-2,2'-bipyridine-κ2N,N')iron(II)]-di-μ-azido-κ2N1:N3-[(5,5'-dimethyl-2,2'-bipyridine-κ2N,N')iron(II)]-di-μ-azido-κ2N1:N1], [Fe(N3)2... Show moreThe title metal-organic polymer, catena-poly[[(5,5'-dimethyl-2,2'-bipyridine-κ2N,N')iron(II)]-di-μ-azido-κ2N1:N3-[(5,5'-dimethyl-2,2'-bipyridine-κ2N,N')iron(II)]-di-μ-azido-κ2N1:N1], [Fe(N3)2(C12H12N2)]n, features alternating μ-1,1 (end-on mode of coordination) and μ-1,3 (end-to-end mode of coordination) double azide bridges, forming chains running in the [100] direction. The octahedral coordination geometry around the FeII centre is completed by a bidentate 5,5'-dimethyl-2,2'-bipyridine ligand. Two polymorphs for this compound were obtained from the crude reaction product, the first in the space group P-1 and the other in P21/c. The molecular and crystal structures are very similar for both forms, the main difference being that the eight-membered Fe(μ-1,3-N3)2Fe metallacycle formed with end-to-end azide ligands has a nearly flat conformation in the triclinic form and a chair conformation in the monoclinic form. In spite of this geometric difference, both forms have the same density, the same packing index and similar arrangements of the one-dimensional chains in the crystal. As a consequence, they also share very similar Hirshfeld surfaces and fingerprint plots. However, a density functional theory (DFT) computational study showed that the monoclinic form is more stable than the triclinic form by ca 30.5 kJ mol-1. Show less
The synthesis, characterization, crystal structure and detailed magnetic properties of a pyrazine (pyz) and azido (N3) bridged cobalt(II) compound of formula [Co(N3)2(pyz)] (1) are reported.... Show moreThe synthesis, characterization, crystal structure and detailed magnetic properties of a pyrazine (pyz) and azido (N3) bridged cobalt(II) compound of formula [Co(N3)2(pyz)] (1) are reported. Compound 1 shows a layered structure formed by Co(II) chains with double μ-N3(κN1,N1) bridges that are further connected by μ-(pyrazine-κN1,N4) bridges. The layers present weak van der Waals interactions between azido terminal groups. The magnetic properties show the presence of a metamagnetic behaviour in 1 with two critical fields of 200 and 400 mT at low temperatures. AC magnetic measurements show the presence of a long-range 2D ferromagnetic order at Tc ≈ 8.0-7.0 K for dc fields above 200 mT and a long-range 3D ferromagnetic order at Tc ≈ 4.5 K for dc fields above 400 mT. Show less
Chemical names can be so long that, when a manuscript is printed, they have to be hyphenated/divided at the end of a line. Many names already contain hyphens, but in some cases, using these hyphens... Show moreChemical names can be so long that, when a manuscript is printed, they have to be hyphenated/divided at the end of a line. Many names already contain hyphens, but in some cases, using these hyphens as end-of-line divisions can lead to illogical divisions in print, as can also happen when hyphens are added arbitrarily without considering the 'chemical' context. The present document provides guidelines for authors of chemical manuscripts, their publishers and editors, on where to divide chemical names at the end of a line, and instructions on how to avoid these names being divided at illogical places. Readability and chemical sense should prevail when authors insert hyphens. The software used to convert electronic manuscripts to print can now be programmed to avoid illogical end-of-line hyphenation and thereby save the author much time and annoyance when proofreading. The Recommendations also allow readers of the printed article to determine which end-of-line hyphens are an integral part of the name and should not be deleted when 'undividing' the name. These Recommendations may also prove useful in languages other than English. Show less
Merkul, E.; Muns, J.A.; Sijbrandi, N.J.; Houthoff, H.‐J.; Nijmeijer, B.; Rheenen, G. van; ... ; Dongen, G.A.M.S. van 2020
The Pt-II linker [ethylenediamineplatinum(II)](2+), coined Lx, has emerged as a novel non-conventional approach to antibody-drug conjugates (ADCs) and has shown its potential in preclinical in... Show moreThe Pt-II linker [ethylenediamineplatinum(II)](2+), coined Lx, has emerged as a novel non-conventional approach to antibody-drug conjugates (ADCs) and has shown its potential in preclinical in vitro and in vivo benchmark studies. A crucial improvement of the Lx conjugation reaction from initially <15 % to ca. 75-90 % conjugation efficiency is described, resulting from a systematic screening of all relevant reaction parameters. NaI, a strikingly simple inorganic salt additive, greatly improves the conjugation efficiency as well as the conjugation selectivity simply by exchanging the leaving chloride ligand on Cl-Lx-drug complexes (which are direct precursors for Lx-ADCs) for iodide, thus generating I-Lx-drug complexes as more reactive species. Using this iodide effect, we developed a general and highly practical conjugation procedure that is scalable: our lead Lx-ADC was produced on a 5 g scale with an outstanding conjugation efficiency of 89 %. Show less
A brief historic overview and analysis is presented of the almost 9000 scientific articles that have appeared in the Journal of Inorganic Biochemistry (JIB) and its predecessor (Bioinorganic... Show moreA brief historic overview and analysis is presented of the almost 9000 scientific articles that have appeared in the Journal of Inorganic Biochemistry (JIB) and its predecessor (Bioinorganic Chemistry), since 1973. This overview has a focus on the different topics, in particular on the different elements of the Periodic Table and on papers that have received very large numbers of citations. Over the whole period, copper has been the element occurring in most publications (almost 1800, which is 20%), followed by iron which occurs in some 12% of all papers. Other favorite elements are zinc, platinum and ruthenium. The worldwide origin of papers published in JIB has been analyzed as well, showing a quite evenly worldwide distribution, with just a few exceptions. Trends in selected scientific topics over time (first 10 years; last 25 years, last 10 years) are also discussed. Also authors and institutes with the largest number of papers published in JIB have been detected. The numerical information is based on an analysis of the Web of Science with a cutoff date around July 1, 2020. Show less
Komeda, S.; In, Y.; Tomoo, K.; Minoura, K.; Sato, T.; Reedijk, J.; ... ; Chikuma, M. 2019
The reaction of the anticancer azolato-bridged dinuclear platinum(II) compound [{cis-Pt(NH3)(2)}(2)(mu-OH)(mu-1,2,3-triazolato-N1,N2)](NO3)(2) (AMTA) in 0.2 M DCl-D2O solution was monitored at 298... Show moreThe reaction of the anticancer azolato-bridged dinuclear platinum(II) compound [{cis-Pt(NH3)(2)}(2)(mu-OH)(mu-1,2,3-triazolato-N1,N2)](NO3)(2) (AMTA) in 0.2 M DCl-D2O solution was monitored at 298 K using H-1 NMR spectroscopy. Acid hydrolysis of AMTA first provided a dinuclear Pt(II) cationic species [{cis-Pt(NH3)(2)Cl}(2)(mu-1,2,3-triazolato-N1,N2)](+) (intermediate A) which then turned into [{cis-Pt(NH3)(2)Cl}(2)(mu-1,2,3-triazolato-N1,N3)](+) (intermediate B) by migration of a Pt(II) ion, initially bound to N2, to N3. Hence, intramolecular ligand substitution of N3 for N2 occurred after substitution of two chloride ligands for the hydroxido bridge. Under the reaction conditions, the intermediate A and B were unambiguously detected, and both or either of the intermediate species then dimerized by a substitution of the chlorido ligand by N3 or N2 of a partner molecule to yield an unprecedented tetranuclear Pt(II) compound [{cis-Pt(NH3)(2)Cl}mu-{cis-Pt(NH3)(2)}(2)(mu-1,2,3-triazolato-N2,N3)(2)-N1,N1']Cl-2(NO3)(2) (compound 1), whose 3D structure has been determined by X-ray crystal analysis. The fact that all triazolate nitrogen atoms coordinated to 3 different Pt(II) ions indicates that 1,2,3-triazolate derivatives could be important as a unique tridentate building block for metal-organic framework. Show less
Addala, A.; Poupon, M.; Bernès, S.; Kürkçüoglu, G.S.; Liu, X.; Lehchili, F.; ... ; Reedijk, J. 2019
The synthesis, characterization and 3D structure determination of Zinc and Cadmium compounds are reported, containing the non-chelating bidentate ligand 4,4'-bipyridine and the anions 1,1,3,3... Show moreThe synthesis, characterization and 3D structure determination of Zinc and Cadmium compounds are reported, containing the non-chelating bidentate ligand 4,4'-bipyridine and the anions 1,1,3,3-tetracyano-2-propoxy-propenide (tcnopr) or 1,1,3,3-tetracyano-2-ethoxy-propenide (tcnoet). The structures consist of linear chains (1D) built from metal ions and 4,4'-bipyridine, where the octahedral coordination around the metals is completed by two trans anions tcnoet (or tcnopr), and two trans-oriented water molecules. Weak interchain interactions are present, based on hydrogen bonds between the water ligands (both hydrogens are involved) and two CN groups of two nearby other chains. Metal-ligand distances appear as uneventful. For the same anion, the Zn and Cd compounds are isomorphous. Possible decomposition of the compounds has been investigated in the temperature range 30-800 degrees C in a static air atmosphere. Thermal analysis studies (TG, DTG, DTA) show that the axial water ligands for all three compounds are gradually lost upon heating above 60 degrees C to about 170 degrees C. Luminescence properties, recorded as powders, are reported as well, and these appear as strong for the Cd compound I, when irradiated at 390 nm, extremely weak for the Cd compound II, when irradiated at wavelengths from 300-400 nm, and moderately weak for the Zn compound III when irradiated at 385 nm. (C) 2019 The Author(s). Published by Elsevier Ltd. Show less
The synthesis, characterization, structure and magnetic properties of a hexametallic mixed-metal iron(III)-cobalt(III) compound are described. The compound has been characterized by standard... Show moreThe synthesis, characterization, structure and magnetic properties of a hexametallic mixed-metal iron(III)-cobalt(III) compound are described. The compound has been characterized by standard spectroscopic and analytical methods to determine its composition. Single-crystal X-ray diffraction has shown that the asymmetric unit consists of discrete dinuclear dicationic units of {(mu-oxido-mu-[sulfato-O1,O2])bis[tris(2-pyridyl-methyl)amineiron(III)]}(2+), herein designated as Fe12, and two half-dinuclear dianionic units of {(mu-oxido)bis[(mu-cyanido-kappa N-pentacyanidocobaltato(III))(tris(2-pyridyl-methyl)-amine)iron(III)]}(2-) units, herein designated as Fe33a and Fe44b, generating the overall composition Co2Fe4O2(C-N)(12)(tpa)(4), 1, where tpa is tris(2-pyridyl-methyl)amine. X-ray structural results and thermogravimetric and differential scanning calorimetry measurements also indicate that the compound, depending upon its history, may contain up to nine interstitial waters of hydration, herein designated as 1(H2O)(9).In the dinuclear dicationic unit, the bridging Fe-O-Fe bond in Fe12 is bent and there is also an FeOSOFe sulfato-based bridge with an angle of 132.8 degrees. In contrast, in the two dinuclear dianionic units, Fe33a and Fe44b, the Fe-O-Fe bond angle is crystallographically constrained to be 180 degrees. The Co-C-N-Fe bonds are almost co-linear, with Co-C-N angles of 176 degrees and C-N-Fe angles of 169 degrees. In each species the tpa ligand is tripodal tetradentate with the tertiary amine trans to the sulfato ligand or to the cyanide ligand in the dianions or the bridged oxido ligand in the dications. Bond lengths and angles are all in the typical range for Fe(III) and Co(III) compounds.The magnetic behavior of 1(H2O)(9), obtained upon cooling from 300 to 2 K, reveals a strong antiferromagnetic interaction between the Fe(III) ions in each dinuclear unit. Attempts to discriminate between the two Fe(III) dinuclear units in 1(H2O)(9) have in all cases led to two very different Heisenberg isotropic exchange coupling constants, namely J = -220(2) and -716(32) cm(-1) for 1(H2O)(9); i.e. one of the dinuclear units, probably the Fe12 unit, is so strongly antiferromagnetically coupled that it is close to diamagnetic between 2 and ca. 250 K and has a Heisenberg S = 0 ground state. (C) 2018 Elsevier Ltd. All rights reserved. Show less
In this perspective the impact of the completion of the 7th row up to Z = 118, by the addition of four new elements in the periodic table - nihonium, moscovium, tennessine and oganesson - is... Show moreIn this perspective the impact of the completion of the 7th row up to Z = 118, by the addition of four new elements in the periodic table - nihonium, moscovium, tennessine and oganesson - is described. Also the methods of how to "synthesize" new chemical elements, and the methods and difficulties of verifying such new elements are briefly discussed. Some speculations are presented about possible new element discoveries in the coming years.Finally, the pathway of how the IUPAC names of the new elements are determined, are presented and illustrated by the most recent 4 additions of new elements. (C) 2017 The Author. Published by Elsevier Ltd. Show less
Lehchili, F.; Setifi, F.; Liu, X.; Saneei, A.; Kucerakova, M.; Setifi, Z.; ... ; Reedijk, J. 2017
New first-row transition-metal compounds with the ligand norharmane (9H-Pyrido[3,4-b]indole; Hnor) are reported. The compounds have the general formula [M(LL)(Hnor)(NO3)(2)](MeOH)(0-1) (M = Co, Ni,... Show moreNew first-row transition-metal compounds with the ligand norharmane (9H-Pyrido[3,4-b]indole; Hnor) are reported. The compounds have the general formula [M(LL)(Hnor)(NO3)(2)](MeOH)(0-1) (M = Co, Ni, Cu, Zn; LL 2,2'-bipyridyl (bpy), 1,10-phenanthroline (phen)) and have been characterized by physical and analytical methods. X-ray structural analysis revealed that the compound of formula [Cu(phen)(Hnor)(NO3)(2)], (1) has a distorted 6-coordinated octahedrally-based geometry, with a planar-based [CuN3O] core, where Cu-L varies between 1.99 and 2.04 angstrom and two weak axial Cu-O contacts (2.209 and 2.644 angstrom) from two different nitrates. Based on spectroscopic similarities, the other compounds appear to have the same or very similar coordination geometries. The compounds showed clear cell growth inhibitory effects in two different cancer cell lines in vitro, with the copper and zinc complexes being the most toxic and in fact almost comparable to cisplatin. Flow-cytometry analysis confirmed induction of apoptosis in cancer cells treated with the compounds. Interestingly, co-incubation of the cells with metal complexes and CuCl2 induced an increase in the cytotoxic effects, most likely due to the conversion of the metal compounds in the corresponding, and most active, copper analogues. (C) 2016 Elsevier Inc. All rights reserved. Show less
Setifi, Z.; Ghazzali, M.; Glidewell, C.; Perez, O.; Setifi, F.; Gomez-Garcia, C.J.; Reedijk, J. 2016
The synthesis, characterization, single crystal structure and magnetic properties of the compound [(CuN3(OH2))(2)(adp)](n) (1) are presented, in which adp stands for the adipate(2-) anion. This... Show moreThe synthesis, characterization, single crystal structure and magnetic properties of the compound [(CuN3(OH2))(2)(adp)](n) (1) are presented, in which adp stands for the adipate(2-) anion. This compound consists of layers containing chains of six-coordinated Cu(II) ions; the chains are connected by mu(4)-adipate anions. The magnetically interesting part of the compound is the Cu(II) chain, built from 3 bridging ligands, i.e. a water ligand, an azide anionic ligand bridging by using a terminal N atom to connect 2 Cu(II) ions, and one symmetrically bridging carboxylato group of adipate; the other end of the tetradentate adipate anions symmetrically connect the chains, forming the layers.From the magnetic point of view the compound is considered as a Cu(II) chain with a quite unusual, symmetrical water bridge, the mu-syn-syn carboxylate and the mu-N-3 bridge. The bridging water also hydrogen bonds to a terminal N of a nearby azido ligand. Magnetic susceptibility measurements show that 1 presents moderate ferromagnetic intrachain interactions (J(chain), = +38.4 cm(-1)) with a metamagnetic behaviour for the inter-chain interaction with a critical field of 0.7 T. (C) 2016 Elsevier Ltd. All rights reserved. Show less
A brief personal account is given on how I observed and enjoyed studying metal-ion nucleic-acid binding over the last 40 years, based on contributions from my own group and from our collaborators... Show moreA brief personal account is given on how I observed and enjoyed studying metal-ion nucleic-acid binding over the last 40 years, based on contributions from my own group and from our collaborators and competitors.Metal ions do bind to ligands, and the nucleic acids not only can act as metal-binding ligands, but also as hydrogen-bonding species, as typically known for Watson-Crick base pairs. In the study of metal nucleic acid binding, coordination and hydrogen bonding do often occur together and may act synergistically. In this account I will highlight a selection of our most important findings within the context of this special issue. (C) 2015 Elsevier B.V. All rights reserved. Show less
Khan, R.A.; Dielmann, F.; Liu, X.; Hahn FE, Al-Farhan, K.; Alsalme, A.; Reedijk, J. 2016
Three isomorphous compounds have been prepared, i.e. [Cu-I(PPh3)(2)(Hnor)(I)], [Cu-I(PPh3)(2)(Hnor)Cl] and [Cu-I(PPh3)(2)(Hnor)Br]. The compounds are tetrahedrally coordinated, as deduced from the... Show moreThree isomorphous compounds have been prepared, i.e. [Cu-I(PPh3)(2)(Hnor)(I)], [Cu-I(PPh3)(2)(Hnor)Cl] and [Cu-I(PPh3)(2)(Hnor)Br]. The compounds are tetrahedrally coordinated, as deduced from the single-crystal X-ray diffraction analysis of the iodide compound. The chloride and bromide compounds were found to be isomorphous. Significant twinning hampered a detailed X-ray diffraction study of the bromide derivative. All three compounds are highly luminescent in the solid state at room temperature and at 100 K. In addition, in acetonitrile (solution) at room temperature the compounds are luminescent. (C) 2016 Elsevier Ltd. All rights reserved. Show less
A procedure is proposed to name new chemical elements. After the discovery of a new element is established by the joint IUPAC-IUPAP Working Group, the discoverers are invited to propose a name and... Show moreA procedure is proposed to name new chemical elements. After the discovery of a new element is established by the joint IUPAC-IUPAP Working Group, the discoverers are invited to propose a name and a symbol to the IUPAC Inorganic Chemistry Division. Elements can be named after a mythological concept, a mineral, a place or country, a property or a scientist. After examination and acceptance by the Inorganic Chemistry Division, the proposal follows the accepted IUPAC procedure and is then ratified by the Council of IUPAC. This document is a slightly amended version of the 2002 IUPAC Recommendations; the most important change is that the names of all new elements should have an ending that reflects and maintains historical and chemical consistency. This would be in general "-ium" for elements belonging to groups 1-16, i.e. including the f-block elements, "-ine" for elements of group 17 and "-on" for elements of group 18. Show less
Jaafar, M.; Liu, X.; Dielmann, F.; Hahn, F.E.; Al-Farhan, K.; Alsalme, A.; Reedijk, J. 2016
Four new compounds containing the (chlorido)((2-x))(cyanido)(x)argentate(I) anion (x = 2, 1.63, 1 and 0.5) are reported. Their solid-state structures with the monocation PPN, bis(triphenylphosphane... Show moreFour new compounds containing the (chlorido)((2-x))(cyanido)(x)argentate(I) anion (x = 2, 1.63, 1 and 0.5) are reported. Their solid-state structures with the monocation PPN, bis(triphenylphosphane) iminium, are described; in a few cases the products also contain solvent molecules. The compounds have the formula (PPN)(2)[Ag2Cl3(CN)], (PPN)[Ag(CN)Cl](CH2Cl2) and (PPN)[Ag(CN)(1.63)Cl-0.37](hexane)(0.5) and (PPN)[Ag(CN)(2)] (CH2Cl2). Apart from the molecular structures and the synthetic process, also the solid-state luminescence has been studied.In the case of (PPN)(2)[Ag2Cl3(CN)], the silver ions are pseudo-trigonally coordinated, with 2 chloride bridges between the Ag+ ions. The terminal Cl and terminal CN ligands are disordered over two positions, but only a single C-13 NMR signal is observed for the cyanide ligands of this compound. The compound (PPN)[Ag(CN)(2)] serves as a reference compound and contains the linear [Ag(CN)(2)] unit.The compound with CN/Cl = 1.0 shows disorder of the [AgCl(CN)] unit, and also in the compounds with other CN/Cl ratios, disorder among the Cl - and CN - ligands is seen. The Ag+ ion is linearly coordinated by two ligands in these two cases, and for cyanides normal Ag-C bond lengths are observed in both cases (1.97-1.99 angstrom). The [Ag(CN)(2)] anion is linear and uneventful. The PPN cation has normal bond lengths in all 4 compounds and no short contacts with other atoms in the lattice are observed. The luminescence properties of the new compounds were explored as solid powders. Only one of the compounds (compound 2, with x = 1) shows luminescence under excitation. The other three compounds do not show emission when irradiated at 320 nm, 350 nm or 380 nm. (C) 2015 Elsevier B. V. All rights reserved. Show less
A very unusual Cu(II) compound of formula [Cu(mqmp)(2)(ClO4)(2)] was synthesized in situ from a one-pot reaction between copper(II) perchlorate and a Schiff base ligand, 2-methoxy-6-((quinolin-3... Show moreA very unusual Cu(II) compound of formula [Cu(mqmp)(2)(ClO4)(2)] was synthesized in situ from a one-pot reaction between copper(II) perchlorate and a Schiff base ligand, 2-methoxy-6-((quinolin-3-ylimino) methyl)phenol, abbreviated mqmp. The resulting compound, bearing positively charged side groups was characterized using single-crystal X-ray diffraction, elemental analysis, electrospray-ionization mass spectrometry (ESI-MS), infrared spectroscopy (IR), ligand-field (LF) spectroscopy, and powder electron paramagnetic resonance (EPR) spectroscopy. The coordination chromophore consists of tetragonal [CuN2O2O2'] units. The compound shows a step-like molecular assembly assisted by hydrogen-bond interactions from -NH+ to ClO4- between the neighbouring molecules. The presence of pyridinic nitrogens bearing a H+ ("hydron") on the quinoline unit is quite unusual, and was validated with computational studies which clearly suggested that this hydronated nitrogen stabilizes the structure by 164 kJ mol(-1) compared to the hydronated phenolic version of the structure. (C) 2016 Elsevier Ltd. All rights reserved. Show less
![Concomitant dimorphism in poly[di-μ-azido-(5,5′-dimethyl-2,2′-bipyridine)iron(II)]](/sites/all/modules/custom/islandora_solr_search/images/defaultimg.png?solr_nav%5Bid%5D=d885a52f3834ff1431ff&solr_nav%5Bpage%5D=0&solr_nav%5Boffset%5D=0)
![A rare example of a double metamagnetic transition leading to 2D and 3D long-range order in the two-dimensional pyrazine- and azido-bridged cobalt(ii) compound [Co(pyz)(N3)2]](/sites/all/modules/custom/islandora_solr_search/images/defaultimg.png?solr_nav%5Bid%5D=d885a52f3834ff1431ff&solr_nav%5Bpage%5D=0&solr_nav%5Boffset%5D=1)
