段階的プロトン脱離に伴う電子状態変化を示す金属錯体の研究

筑波大学 (University of Tsukuba)201

Oxalate-bridged heterometallic chains with monocationic dabco derivatives

A series of bimetallic oxalate-bridged one-dimensional chains with monocationic dabco derivatives, ({R-dabco}[M(solv)2][Cr(ox)3]·n(solv)) (dabco = 1,4-diazabicyclo[2.2.2]octane, H2ox = oxalate; R = H, M = Co (1); R = H, M = Zn (2); R = Bu, M = Co (3); R = Bu, M = Zn (4)) were synthesized. All compounds have one-dimensional zig-zag chain structures with R-dabco cations located between chains. Cryomagnetic studies reveal that 1 and 3 showed intrachain ferromagnetic interactions between Co(II) and Cr(III) ions and metamagnetic behaviour due to interchain antiferromagnetic interactions. Permittivity measurements on compound 4 indicate specific paraelectronic relaxation behaviour originating from the rotational motion of the dabco alkyl substituent

A Brønsted ligand molecular switch with five accessible states

A mononuclear Fe(II) complex, prepared with a Brønsted diacid ligand, H2L (H2L = 2-[5-phenyl-1H-pyrazole-3-yl] 6benzimidazole pyridine), shows switchable physical properties and was isolated in five different electronic states. The spin crossover (SCO) complex, [FeII(H2L)2](BF4)2 (1A), exhibits abrupt spin transition at T1/2 = 258 K, and treatment with base yields a deprotonated analogue [FeII(HL)2] (1B), which shows gradual SCO above 350 K. A range of ferric analogues were also characterized. [FeIII(HL)(H2L)](BF4)Cl (1C) has an S = 5/2 spin state, while the deprotonated complexes [FeIII(L)(HL)], (1D), and (TEA)[FeIII(L)2], (1E) exist in the low-spin S = 1/2 state. The electronic properties of the five complexes were fully characterized and we demonstrate in situ switching between multiple states in both solution and the solid-state. The versatility of this simple mononuclear system illustrates how proton donor/acceptor ligands can vastly increase the range of accessible states in switchable molecular devices

Substituent dependence on the spin crossover behaviour of mononuclear Fe(ii) complexes with asymmetric tridentate ligands

Three mononuclear iron(II) complexes of the formula [FeII(H2L1-3)2](BF4)2.x(solv.) (H2L1-3 = 2-[5-(R-phenyl)-1H-pyrazole-3-yl] 6-benzimidazole pyridine; H2L1: R = 4-methylphenyl, H2L2, R = 2,4,6-trimethylphenyl, H2L3, R = 2,3,4,5,6pentamethylphenyl) (1, H2L1; 2, H2L2; 3, H2L3) with asymmetric tridentate ligands (H2L1-3) were synthesized and their structures and magnetic behaivor investigated. Significant structural distortions of the dihedral angles between phenyl and pyrazole groups were observed and found to depend on the nature of the substituent groups. Cryomagnetic studies reveal that 1 and 2 show gradual spin crossover behavior, while 3 remains in the high spin state between 1.8 and 300 K

An antiferromagnetically coupled heterometal Cu6Fe wheel

A heterometal Cu6Fe wheel molecule, [CuII6FeIII(HL)6- (OH)2(OCH3)4](NO3)3¢6H2O (1¢6H2O) (H2L = 1-(2-pyridine) 3-(2-pyrrole)acetylacetone) was synthesized by the one-pot reaction of H2L with copper and iron sources. X-ray structural analysis reveals that the heptanuclear wheel cluster consists of a central Fe(III) ion surrounded by six Cu(II) ions, linked through methoxo- and hydroxo-bridges. Cryomagnetic studies indicate intramolecular antiferromagnetic interactions were operative

Predictive Value of the Cardio-Ankle Vascular Index for Cardiovascular Events in Patients at Cardiovascular Risk

BACKGROUND: Arterial stiffness is an important predictor of cardiovascular events; however, indexes for measuring arterial stiffness have not been widely incorporated into routine clinical practice. This study aimed to determine whether the cardio-ankle vascular index (CAVI), based on the blood pressure-independent stiffness parameter beta and reflecting arterial stiffness from the origin of the ascending aorta, is a good predictor of cardiovascular events in patients with cardiovascular disease risk factors in a large prospective cohort. METHODS AND RESULTS: This multicenter prospective cohort study, commencing in May 2013, with a 5-year follow-up period, included patients (aged 40-74 years) with cardiovascular disease risks. The primary outcome was the composite of cardiovascular death, nonfatal stroke, or nonfatal myocardial infarction. Among 2932 included patients, 2001 (68.3%) were men; the mean (SD) age at diagnosis was 63 (8) years. During the median follow-up of 4.9 years, 82 participants experienced primary outcomes. The CAVI predicted the primary outcome (hazard ratio, 1.38; 95% CI, 1.16-1.65; P CONCLUSIONS: This large cohort study demonstrated that the CAVI predicted cardiovascular events

都市近郊の里山地域における地域協働型デザイン教育モデルの実践的構築

　本研究は、都市近郊に活用されないまま偏在する緩衝緑地、圃場、里山をフィールドとして、環境デザイン、プロダクト・インテリアデザイン、ソーシャルアートの見地から、持続可能な地域協働型のデザイン教育モデルを構築することを目的としている。　具体的には、研究学園都市周辺地域の荒廃した保安林や緑地、共生ゾーン集落の里山、国営明石海峡公園神戸地区、キーナの森公園、神出里づくり地域などの活用されないまま残る緑地、里山、圃場地等において、自然生態、歴史、文化、環境、空間、素材などの調査活動および、立地環境や整備派生材を生かしたワークショップの企画・運営を実践し、地域協働型のデザイン教育モデルを試行した 。　令和3年度においては、調査対象地における、①地理的・歴史的・文化的側面からのランドスケープおよび建造物調査、②樹木や希少植物などの植生調査を中心に、既存資料などの集約を行い、対象地の利用価値について検討する基礎資料を作成した。実証実験では、地域の教育機関と連携した体験学習会を実施したほか、大学・大学院授業において里山をテーマとした制作を行った。また、調査や実験のプロセス、結果をリアルタイムに映像化・可視化し、SNS等によって情報公開を行った。　The purpose of this research is to construct a sustainable collaborative regional design education model from the perspectives of environmental design, product and interior design, and social art, using buffer green spaces, fields, and satoyama, which remain unutilized and unevenly distributed in the urban suburbs, as fields.　In 2021, the project focused on (1) landscape and building surveys from geographical, historical, and cultural perspectives, (2) vegetation surveys of trees and rare plants,　and compiled existing materials to create basic data for　considering the us e value of the target sites. In the　demonstration experiment, hands on learning sessions were　conducted in collaboration with local educational institutions,　and satoyama themed productions were conducted in university and graduate school classes. In addition, the process and results of the surveys and experiments were visualized in real time and made public through SNS and other means