Probing the Chemical Functionalization of Single‐Walled Carbon Nanotubes with Multiple Carbon Ad‐Dimer Defects

Drying‐tube‐shaped single‐walled carbon nanotubes (SWCNTs) with multiple carbon ad‐dimer (CD) defects are obtained from armchair (n,n,m) SWCNTs (n=4, 5, 6, 7, 8; m=7, 13). According to the isolated‐pentagon rule (IPR) the drying‐tube‐shaped SWCNTs are unstable non‐IPR species, and their hydrogenated, fluorinated, and chlorinated derivatives are investigated. Interestingly, chemisorptions of hydrogen, fluorine, and chlorine atoms on the drying tube‐shaped SWCNTs are exothermic processes. Compared to the reaction energies for binding of H, F, and Cl atoms to perfect and Stone–Wales‐defective armchair (5,5) nanotubes, binding of F with the multiply CD defective SWCNTs is stronger than with perfect and Stone–Wales‐defective nanotubes. The reaction energy for per F₂ addition is between 85 and 88 kcal mol^?1 more negative than that per H₂ addition. Electronic structure analysis of their energy gaps shows that the CD defects have a tendency to decrease the energy gap from 1.98–2.52 to 0.80–1.17 eV. After hydrogenation, fluorination, and chlorination, the energy gaps of the drying‐tube‐shaped SWCNTs with multiple CD defects are substantially increased to 1.65–3.85 eV. Furthermore, analyses of thermodynamic stability and nucleus‐independent chemical shifts (NICS) are performed to analyze the stability of these molecules.     

Extraction of (9,8) Single‐Walled Carbon Nanotubes by Fluorene‐Based Polymers

Selective polymer wrapping is a promising approach to obtain high‐chiral‐purity single‐walled carbon nanotubes (SWCNTs) needed in technical applications and scientific studies. We showed that among three fluorene‐based polymers with different side‐chain lengths and backbones, poly[(9,9‐dihexylfluorenyl‐2,7‐diyl)‐co‐(9,10‐anthracene)] (PFH‐A) can selectively extract SWCNTs synthesized from the CoSO₄/SiO₂ catalyst, which results in enrichment of 78.3 % (9,8) and 12.2 % (9,7) nanotubes among all semiconducting species. These high‐chiral‐purity SWCNTs may find potential applications in electronics, optoelectronics, and photovoltaics. Furthermore, molecular dynamics simulations suggest that the extraction selectivity of PFH‐A relates to the bending and alignment of its alkyl chains and the twisting of its two aromatic backbone units (biphenyl and anthracene) relative to SWCNTs. The strong π–π interaction between polymers and SWCNTs would increase the extraction yield, but it is not beneficial for chiral selectivity. Our findings suggest that the matching between the curvature of SWCNTs and the flexibility of the polymer side chains and the aromatic backbone units is essential in designing novel polymers for selective extraction of (n,m) species.     

Theoretical investigation of the stability,electronic and magnetic properties of thiolated single‐wall carbon nanotubes

The addition of SH and OH groups to single‐wall carbon nanotubes (SWCNTs) was investigated employing first principles calculations. In the case of the semiconducting (10, 0) SWCNT the SWCNT‐SH binding energy is weak, 2–4 kcal/mol. However, for the metallic (5, 5) SWCNT it is larger, 7–9 kcal/mol. Thus metallic SWCNTs seem to be more reactive to SH than the semiconducting ones. Indeed, the (6, 6) SWCNT is more reactive to SH than the (10, 0) SWCNT, by 2–3 kcal/mol, something that can be explained only considering the electronic structure of the tube, because the (6, 6) has a larger diameter. The binding energies are larger for the addition of the OH group, 25 and 30 kcal/mol for the (10, 0) and (5, 5) SWCNTs, respectively. When a single OH or SH group is attached to the metallic SWCNTs, we observe important changes in the DOS at the Fermi level. However, when multiple SH groups are attached, the changes in the electronic and magnetic properties depend on the position of the SH groups. The small binding energy found for the SH addition indicates that the successful functionalization of SWCNTs with SH, SCH₃, and S(CH₂)_nSH groups is mostly due to the presence of defects created after acid treatment and to a minor extent by the metallic tubes present in the samples. Perfect semiconducting SWCNTs showed very low reactivity against the SH group. © 2008 Wiley Periodicals, Inc. Int J Quantum Chem, 2009     

Highly Efficient Multiphoton‐Pumped Frequency‐Upconversion Stimulated Blue Emission with Ultralow Threshold from Highly Extended Ladder‐Type Oligo(p‐phenylene)s

A series of highly extended π‐conjugated ladder‐type oligo(p‐phenylene)s containing up to 10 phenyl rings with (L)‐Ph(n)‐NPh (n=7–10) or without diphenylamino endcaps (L)‐Ph(n) (n=7 and 8) were synthesized and investigated for their multiphoton absorption properties for frequency upconverted blue ASE/lasing. Extremely large two‐photon absorption (2PA) cross‐sections and highly efficient 2PA ASE/lasing with ultralow threshold were achieved. (L)‐Ph(10)‐NPh exhibits the highest intrinsic 2PA cross‐section of 3643 GM for a blue emissive organic fluorophore reported so far. The record‐high 2PA pumped ASE/lasing efficiency of 2.06 % was obtained by un‐endcapped oligomer, (L)‐Ph(8) rather than that with larger σ₂, suggesting that a molecule with larger σ₂ is not guaranteed to exhibit higher η₂. All of these oligomers exhibit exceptionally ultralow 2PA pumped ASE/lasing thresholds, among which the lowest 2PA pumped threshold of circa 0.26 μJ was achieved by (L)‐Ph(10)‐NPh.     

Strontium Vanadium Oxide–Hydrides: “Square‐Planar” Two‐Electron Phases

A series of strontium vanadium oxide–hydride phases prepared by utilizing a low‐temperature synthesis strategy in which oxide ions in Sr_n+1V_nO_3n+1 (n=∞, 1, 2) phases are topochemically replaced by hydride ions to form SrVO₂H, Sr₂VO₃H, and Sr₃V₂O₅H₂, respectively. These new phases contain sheets or chains of apex‐linked V³⁺O₄ squares stacked with SrH layers/chains, such that the n=∞ member, SrVO₂H, can be considered to be analogous to “infinite‐layer” phases, such as Sr_1?xCa_xCuO₂ (the parent phase of the high‐T_c cuprate superconductors), but with a d² electron count. All three oxide–hydride phases exhibit strong antiferromagnetic coupling, with SrVO₂H exhibiting an antiferromagnetic ordering temperature, T_N>300 K. The strong antiferromagnetic couplings are surprising given they appear to arise from π‐type magnetic exchange.     

Advantage of the N‐Alkylation Strategy for Retaining the Molecular Planarity for Oligothiophene/Imidazole/1,10‐Phenanthroline‐Based Heterocyclic Semiconducting and Fluorescent Compounds

A family of planar oligothiophene/imidazole/1,10‐phenanthroline (OTIP)‐based heterocyclic, aromatic, semiconducting, and fluorescent compounds with N‐substituted alkyl chains (allyl, n‐butyl, n‐octyl, n‐dodecyl, and n‐cetyl) have been designed and synthesized. They all have specific N‐coordination sites, various donor–acceptor spacers, good molecular planarity, suitable solubility, and high thermal stability. In comparison with conventional double β‐alkylation of the thiophene ring, our results reveal that the single imidazole N‐alkylation strategy for OTIPs has the advantage of maintaining the planarity of the whole molecule, in addition to improving the solubility, which can be clearly verified by the small dihedral angles between adjacent thiophene/imidazole/1,10‐phenanthroline (TIP) rings in eight X‐ray single‐crystal structures. In particular, n‐dodecyl‐ and n‐cetyl‐substituted OTIPs ( 7 and 8 ) with the same molecular length of 2.37 nm (M_W=939 and 1052), show good molecular planarity with the aforementioned dihedral angles of 8.9(5) and 10.4(5)°. Furthermore, special attention has been paid to the physicochemical properties of seven symmetrical OTIPs ( 6 – 8 , 13 – 15 , and 19 ), including two to six thiophene rings in the middle of their molecular structures. To the best of our knowledge, this is the first synthetic, structural, and spectral investigation into the N‐alkylation of OTIP‐based compounds.     

Diradical Character Tuning for the Third‐Order Nonlinear Optical Properties of Quinoidal Oligothiophenes by Introducing Thiophene‐S,S‐dioxide Rings

To create a design guideline for efficient third‐order nonlinear optical (NLO) molecules, the chain‐length (n) dependences of the diradical character y and the longitudinal second hyperpolarizability γ of quinoidal oligothiophenes (QTs), from monomers to octamers, involving thiophene‐S,S‐dioxide rings are investigated by using the density functional theory method. It turns out that the diradical character of the modified QTs is reduced as compared to those of the pristine QTs. By introducing an appropriate number of oxidized rings into the QT framework, intermediate y values can be achieved even in the systems with large values of n, in which the pristine QTs are predicted to have pure diradical character. Such intermediate diradical oligomers are shown to exhibit enhanced γ values as compared to the pristine QTs with the same value for n. From the calculation results, the introduction of the optimal number of thiophene‐S,S‐dioxide rings is predicted to be an efficient chemical modification for optimizing the third‐order NLO properties of open‐shell QTs through tuning the diradical characters.     

Poly(γ‐benzyl‐L‐glutamate)‐functionalized single‐walled carbon nanotubes from surface‐initiated ring‐opening polymerizations of N‐carboxylanhydride

Single‐walled carbon nanotubes (SWCNTs) have been functionalized with poly(γ‐benzyl‐L ‐glutamate) (PBLG) by ring‐opening polymerizations of γ‐benzyl‐L ‐glutamic acid‐based N‐carboxylanhydrides (NCA‐BLG) using amino‐functionalized SWCNTs (SWCNT‐NH₂) as initiators. The SWCNT functionalization has been verified by FTIR spectroscopy and transmission electron microscopy. The FTIR study reveals that surface‐attached PBLGs adopt random‐coil conformations in contrast to the physically absorbed or bulk PBLGs, which exhibit α‐helical conformations. Raman spectroscopic analysis reveals a significant alteration of the electronic structure of SWCNTs as a result of PBLG functionalization. The PBLG‐functionalized SWCNTs (SWCNT‐PBLG) exhibit enhanced solubility in DMF. Stable DMF solutions of SWCNT‐PBLG/PBLG with a maximum SWCNTs concentration of 259 mg L^?1 can be readily obtained. SWCNT‐PBLG/PBLG solid composites have been characterized by differential scanning calorimetry, thermogravimetric analysis, wide/small‐angle X‐ray scattering (W/SAXS), scanning electron microscopy, and polarized optical microscopy for their thermal or morphological properties. Microfibers containing SWCNT‐PBLG and PBLG can also be prepared via electrospinning. WAXS characterization reveals that SWCNTs are evenly distributed among PBLG rods in solution and in the solid state where PBLGs form a short‐range nematic phase interspersed with amorphous domains. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 2340–2350, 2010     

A Main‐Group Element Radical Based One‐Dimensional Magnetic Chain

The first main‐group element radical based one‐dimensional magnetic chain ( 1K )_n was realized by one‐electron reduction of the pyridinyl functionalized borane 1 with elemental potassium in THF in the absence of 18‐crown‐6 (18‐c‐6). The electron spin density of ( 1K )_n mainly resides at the boron centers with a considerable contribution from central benzene and pyridine moieties. The spin centers exhibit an antiferromagnetic interaction as demonstrated by magnetic measurements and theoretical calculations. In contrast, the reduction in the presence of 18‐c‐6 afforded the separated radical anion salt 1K(Crown) , in which the potassium cation was trapped by THF and 18‐c‐6 molecules. Further one‐electron reduction of 1K(Crown) and ( 1K )_n led to the diamagnetic monomer and polymer, respectively.     

Single‐Molecule Magnetism in Three Dy2 Complexes from the Use of a Pentadentate Schiff Base Ligand and Different Benzoates

Three dinuclear dysprosium(III) complexes, [Dy₂L₂(O₂CPh)₂]?2 MeOH ( 1 ), [Dy₂L₂{(2‐NO₂)O₂CPh}₂] ( 2 ), and [Dy₂L₂{(2‐OH)O₂CPh}₂] ? MeOH ? MeCN ( 3 ) (H₂L=N₁,N₃‐bis(4‐chlorosalicyladehyde)diethylenetriamine), have been synthesized and structurally characterized. Complexes 1 – 3 possess similar Ln₂ cores and differ in substituents at the benzyl rings of benzoates. Direct current (dc) magnetic susceptibility studies in the 2–300 K range showed weak antiferromagnetic interactions between two dysprosium(III) ions in 1 – 3 . The alternating current (ac) magnetic susceptibility measurements indicated that they all exhibited SMM behavior. The strategic attachment of the ?NO₂ group (in 2 ) and the ?OH functionality (in 3 ) on the skeleton of the benzoic acid led to subtle variations of the bond lengths and bond angles in the coordination environments of the central dysprosium(III) ions, consequently resulting in the enhancement of the energy barriers for 2 and 3 . Complete‐active‐space self‐consistent field (CASSCF) calculations were employed to rationalize the experimental outcomes. Theoretical calculations confirm the existence of antiferromagnetic interactions in 1 – 3 , and the calculated dc magnetic susceptibility data agree well with those obtained experimentally. The computational results reveal more axial g tensors, as well as higher first excited Kramers doublets in 2 and 3 ; thus resulting in higher energy barriers in compounds 2 and 3 .     

Infinite Coordination Polymers of One‐ and Two‐dimensional Cobalt Acetates

Two coordination polymers of cobalt acetate, [Co₅(O₂CMe)₁₀] ( 1 ) and [Co(O₂CMe)₂(H₂O)] · H₂O ( 2 ), were solvothermally synthesized and characterized by single‐crystal and powder X‐ray diffraction analyses, IR spectroscopy, and elemental analysis. Compound 1 crystallizes in orthorhombic space group Pbcn in two‐dimensional layers, which consist of 12‐membered cobalt rings. Compound 2 crystallizes in monoclinic space group C2/m and exhibits one‐dimensional chains, which are bridged by one water molecule and two acetate ligands in (2.11)‐ and (2.20)‐modes. Preliminary magnetic studies revealed that antiferromagnetic couplings exist in both compounds.     

Six Coordination Polymers based on 4‐(1H‐Imidazol‐1‐yl)phthalic Acid: Structural Diversities,Magnetism and Luminescence Properties

The coordination polymers (CPs), [Ni(L)(H₂O)₄]_n ( 1 ), [Co(HL)₂(H₂O)₂]_n ( 2 ), {[Cu(L)(H₂O)₃] · H₂O}_n ( 3 ), [Mn(L)(H₂O)₂]_n ( 4 ), [Cd(L)(H₂O)₂]_n ( 5 ), and {[Zn₂(L)₂] · H₂O}_n ( 6 ), were solvothermally synthesized by employing the imidazol‐carboxyl bifunctional ligand 4‐(1H‐imidazol‐1‐yl) phthalic acid (H₂L). Single‐crystal X‐ray diffraction indicated that the L^2–/HL^– ligands display various coordination modes with different metal ions in 1 – 6 . Complexes 1 and 2 show one‐dimensional (1D) chain structures, whereas complexes 3 – 6 show 2D layered structures. The magnetic properties of these complexes were investigated. Complexes 1 and 3 indicate weak ferromagnetic interactions, whereas complexes 2 and 4 demonstrate antiferromagnetic interactions. In addition, luminescence properties of 5 and 6 were measured and studied in detail.     

catena‐Poly[[[diaquazinc]‐bis{μ‐N2,N6‐bis[(pyridin‐3‐yl)methyl]pyridine‐2,6‐dicarboxamide}] dinitrate]

In the title compound, {[Zn(C₁₉H₁₇N₅O₂)₂(H₂O)₂](NO₃)₂}_n, the Zn^II cation is located at an inversion centre within a slightly distorted octahedron, ligated by four N atoms from four N²,N⁶‐bis[(pyridin‐3‐yl)methyl]pyridine‐2,6‐dicarboxamide (L) ligands occupying a plane about the Zn^II atom with the two water O atoms perpendicular to that. In the complex molecule, the bidentate bridging L ligands display helical R and S conformers, and link the Zn^II cations into a one‐dimensional centrosymmetric double‐chain structure containing 32‐membered rings. The nitrate anions reside in these rings and are involved in multiple N—H...O hydrogen‐bond interactions. On excitation at 390 nm, the title compound displays a strong blue emission centred at 449 nm. Investigation of the thermal stability shows that the network structure is stable up to 420 K.     

Antiferromagnetic Interactions in 1D Heisenberg Linear Chains of 7‐(4‐Fluorophenyl) and 7‐Phenyl‐Substituted 1,3‐Diphenyl‐1,4‐dihydro‐ 1,2,4‐benzotriazin‐4‐yl Radicals

7‐(4‐Fluorophenyl) and 7‐phenyl‐substituted 1,3‐diphenyl‐1,4‐dihydro‐1,2,4‐benzotriazin‐4‐yl radicals were characterized by X‐ray diffraction analysis and variable‐temperature magnetic susceptibility studies. The radicals pack in 1D π stacks of equally spaced slipped radicals with interplanar distances of 3.59 and 3.67 Å and longitudinal angles of 40.97 and 43.47°, respectively. Magnetic‐susceptibility studies showed that both radicals exhibit antiferromagnetic interactions. Fitting the magnetic data revealed that the behavior is consistent with 1D regular linear antiferromagnetic chain with J=?12.9 cm^?1, zJ′=?0.4 cm^?1, g=2.0069 and J=?11.8 cm^?1, zJ′=?6.5 cm^?1, g=2.0071, respectively. Magnetic‐exchange interactions in benzotriazinyl radicals are sensitive to the degree of slippage, and inter‐radical separation and subtle changes in structure alter the fine balance between ferro‐ and antiferromagnetic interactions.     

Carbo‐biphenyls and Carbo‐terphenyls: Oligo(phenylene ethynylene) Ring Carbo‐mers

Ring carbo‐mers of oligo(phenylene ethynylene)s (OPEn, n=0–2), made of C₂‐catenated C₁₈ carbo‐benzene rings, have been synthesized and characterized by NMR and UV‐vis spectroscopy, crystallography and voltammetry. Analyses of crystal and DFT‐optimized structures show that the C₁₈ rings preserve their individual aromatic character according to structural and magnetic criteria (NICS indices). Carbo‐terphenyls (n=2) are reversibly reduced at ca. ?0.42 V/SCE, i.e. 0.41 V more readily than the corresponding carbo‐benzene (?0.83 V/SCE), thus revealing efficient inter‐ring π‐conjugation. An accurate linear fit of E_1/2^red1 vs. the DFT LUMO energy suggests a notably higher value (?0.30 V/SCE) for a carbo‐quaterphenyl congener (n=3). Increase with n of the effective π‐conjugation is also evidenced by a red shift of two of the three main visible light absorption bands, all being assigned to TDDFT‐calculated excited states, one of them restricting to a HOMO→LUMO main one‐electron transition.     

A reasonable criterion of reactivities at the defective region of single‐walled carbon nanotubes

Defect directional curvature K_D‐def was proposed as a reasonable criterion for the reactivities and adduct structures at the defective region of single‐walled carbon nanotubes (SWCNTs). B3LYP/6‐31G* calculations for the [2 + 1] and [1 + 1] additions of a series of 11‐layer (n, n) (n = 4–8) and six‐layer (10,0) SWCNTs with Stone‐Wales defects showed that the K_D‐def or its mean K_M‐def was a good index to judge the adduct structures and the reactivities. Adducts of the [2 + 1] additions were divided into two types: one was the adduct with the C‐X‐C configuration and corresponding to the large K_D‐def and the large binding energy, and another was the adduct with the closed ?3MR structure and corresponding to the small K_D‐def and the small binding energy. It must be pointed out that, besides mainly relying on the K_D‐def, the adduct structures and the reactivities of the [2 + 1] additions had been weakly affected by topologic structures. The calculated results for the [1 + 1] additions of the 11‐layer (5,5) SWCNT with defect A revealed that the binding energies monotonously increased with the K_M‐def. © 2008 Wiley Periodicals, Inc. Int J Quantum Chem, 2009     

Thermoreversible gelation of helical polypeptide/single‐walled carbon nanotubes and their solid‐state structures

Single‐walled carbon nanotubes (SWCNTs) have been functionalized with poly(γ‐benzyl‐L ‐glutamate)s (PBLGs) having well‐defined polymer molecular weight (M_n = 7.5–21.1 kg·mol^?1) and molecular weight distribution (PDI = 1.05–1.20) by a graft‐to method. Toluene solutions containing 5 wt % free PBLG and variable amounts of PBLG‐functionalized SWCNTs (PBLG‐SWCNTs) form gels at room temperature. Differential scanning calorimetry (DSC) analysis reveals that the gelation occurs thermoreversibly, in accord with previous studies on the pristine PBLG/toluene gels. The heat of gel melting (ΔH_m) is slightly elevated for the composite gels compared with the pristine gel, which suggests enhanced interactions between PBLGs in the former. But the gelation temperatures of the composites are unaffected by the presence of PBLG‐SWCNTs. Small‐angle X‐ray scattering (SAXS) analysis of the composite and pristine gels at different temperatures by the Guinier method suggests that PBLG‐SWCNTs promote interactions between PBLG rods, as indicated by the larger PBLG bundle size with increasing PBLG‐SWCNT content in the gel and the melt state. W/SAXS analysis of the dry gels reveals that PBLG‐SWCNTs induce significant changes in the PBLG packing order, resulting in a nematic phase, in contrast to a weakly ordered smectic C phase containing tilted PBLG rods that is observed in the pristine gel. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

Metallkomplexe mit biologisch wichtigen Liganden. CLXVI Metallkomplexe mit Ferrocenylmethyl‐L‐cysteinat und 1,1′‐Ferrocenylbis‐(methyl‐L‐cysteinat) als Liganden

Metal Complexes of Biologically Important Ligands. CLXVI Metal Complexes with Ferrocenylmethylcysteinate and 1,1′‐Ferrocenylbis‐(methylcysteinate) as Ligands A series of complexes of transition metal ions ( Cr³⁺, Mn²⁺, Co²⁺, Ni²⁺, Cu²⁺, Zn²⁺ ) and of lanthanide ions ( La³⁺, Nd³⁺, Gd³⁺, Dy³⁺, Lu³⁺ ) with the anions of ferrocenylmethyl‐L‐cysteine [(C₅H₅)Fe(C₅H₄CH(R)SCH₂CH(NH₃⁺)CO₂^?] (L¹) and with the dianions of 1,1′‐ferrocenylbis(methyl‐L‐cysteine) [Fe(C₅H₄CH(R)SCH₂CH(NH₃⁺) CO₂^?)₂] (R = H, Me, Ph) (L²) as N,O,S‐donors were prepared. With the monocysteine ferrocene derivative L¹ as ligands complexes [M^IIL¹₂] or [Cr^IIIL¹₂]Cl type complexes are formed whereas the bis(cysteine) ligand L² yields insoluble complexes of type [ML²]_n, presumably as coordination polymers. The magnetic moments of [Mn^IIL²]_n, [Pr^IIIL²]_n(OH)_n and [Dy^IIIL²]_n(OH)_n exhibit “normal” paramagnetism.     

High Magnetic Moments in Manganese‐Doped Silicon Clusters

We report on the structural, electronic, and magnetic properties of manganese‐doped silicon clusters cations, Si_nMn⁺ with n=6–10, 12–14, and 16, using mass spectrometry and infrared spectroscopy in combination with density functional theory computations. This combined experimental and theoretical study allows several structures to be identified. All the exohedral Si_nMn⁺ (n=6–10) clusters are found to be substitutive derivatives of the bare Si_n+1⁺ cations, while the endohedral Si_nMn⁺ (n=12–14 and 16) clusters adopt fullerene‐like structures. The hybrid B3P86 functional is shown to be appropriate in predicting the ground electronic states of the clusters and in reproducing their infrared spectra. The clusters turn out to have high magnetic moments localized on Mn. In particular the Mn atoms in the exohedral Si_nMn⁺ (n=6–10) clusters have local magnetic moments of 4 μ_B or 6 μ_B and can be considered as magnetic copies of the silicon atoms. Opposed to other 3d transition‐metal dopants, the local magnetic moment of the Mn atom is not completely quenched when encapsulated in a silicon cage.     

Ground State Structures,Electronic and Magnetic Properties of ScnFe (n=2–10) Clusters

The authors predict that the magnetic moment of the scandium clusters can not be efficiently enhanced with the encapsulation of Fe atom, which is different from previous works with Fe atom doped in B_n, Si_n, and Ge_n clusters. It was found that starting from n=6, the growth patterns of the ground state structures of the Sc_nFe clusters are dominated by the octahedron structures with Fe atom falling into the center of the host framework. The calculated results manifest that doping of the Fe atom contributes to strengthening the stabilities of the scandium framework. Maximum peaks are observed for clusters of n=3, 6 and 8 on the size dependence of the second‐order energy differences, implying that these clusters possess relatively higher stability. The HOMO‐LUMO gap of the Sc_nFe clusters exhibits an oscillational odd‐even character with the local peaks of n=4, 6 and 8. Especially, there is the largest oscillation of the gap with n=4 and 5. Additionally, the doped Fe atom exhibits the antiferromagnetic alignment at n=4, 5, 7 and 9. Also, the quench of the magnetic moments as n=6, 8 and 10 may be ascribed to the model of close‐shell electrons.