Please use this identifier to cite or link to this item: http://rportal.lib.ntnu.edu.tw:80/handle/20.500.12235/111185
Title: Manganese and Iron Carbonyl Chalcogenide Clusters: Syntheses, Structural Transformations, Exotic Properties, and Computational Studies
Manganese and Iron Carbonyl Chalcogenide Clusters: Syntheses, Structural Transformations, Exotic Properties, and Computational Studies
Authors: 謝明惠
Shieh, Ming-huey
劉郁欣
Liu, Yu-Hsin
Keywords: none
none
Issue Date: 2020
Abstract: 1. Se/Fe/Cu 系統之研究 利用三組件 [Cu(MeCN)4]+、[SeFe3(CO)9]2− 和共軛性或非共軛性之含氮吡啶配子以固態溶劑輔助研磨 (three-component liquid-assisted grinding) 的合成方式,可得一系列結構新穎的混合 SeFe3(CO)9−有機含氮吡啶之一維及二維 Cu(I) 金屬聚合物。此系列聚合物可依 SeFe3(CO)9 之不同的功能而分為三種類型,包含以混合 SeFe3(CO)9−有機含氮吡啶為串聯配子之二維的五層互相貫穿 (5-fold interpenetrating) 聚合物 [(MeCN)(dpy)Cu(μ4-Se)Fe3(CO)9Cu(dpy)0.5]n (1-dpy-2D) 和蜂巢狀 (honeycomb-like) 聚合物[(bpp)Cu(μ4-Se)Fe3(CO)9Cu(bpp)]n (1-bpp-2D);以及利用有機含氮吡啶配子串接輔以 SeFe3(CO)9 保護之一維 Z 字型 (zigzag chain) 聚合物 [(μ3-Se)Fe3(CO)9Cu2(L)]n (L = bpee, 1-bpee-1D; bpea, 1-bpea-1D);和有機含氮吡啶配子串接及 SeFe3(CO)9 垂吊之一維 Z 字型 (zigzag chain) 聚合物 [(μ3-Se)Fe3(CO)9Cu(dpy)Cu(dpy)2]n (1-dpy-1D)。再者,利用溶劑輔助研磨 (LAG) 的方法,可成功引入外加之 [SeFe3(CO)9]2− 和 Cu(I) 以及 dpy 配子並完成非常稀少之非互相貫穿一維聚合物 1-dpy-1D 和五層互相貫穿聚合物 1-dpy-2D 之間的可逆結構轉換。相似的策略亦可成功將一維聚合物 1-bpee-1D 和 1-bpea-1D 轉換至其二維聚合衍生物 [(μ3-Se)Fe3(CO)9Cu(L)Cu(L)1.5]n (L = bpee, 1-bpee-2D; bpea, 1-bpea-2D);以及完成巨環分子型化合物 [{(μ3-Se)Fe3(CO)9Cu2}2(bpp)2] 與其二維聚合物 1-bpp-2D 間的可逆結構轉換。此系列聚合物皆具有低且可調控的半導體能隙,值得注意的是,以混合 SeFe3(CO)9 和共軛阻斷之 bpp 配子串接的聚合物 1-bpp-2D 具有異常低之能隙 (1.58 eV),係透過非典型的 C−H···O(carbonyl) 以及芳香性之 C−H···π 弱作用力於團簇物骨架結構中進行有效的電子傳導。此外,低能隙之聚合物 1-bpp-2D、1-bpea-2D 和 1-dpy-1D 具有特殊的光降解活性,其中 1-bpp-2D 擁有最優良的光降解特性,可進一步分解硝基苯衍生物以及有機染劑。另一方面,聚合物 1-dpy-2D、1-bpp-2D、1-bpea-2D 和 1-dpy-1D 皆擁有稀有的短波長紅外光放光特性。這些特別的結構−特性之間的關係可藉由 X-ray 結構分析和泛含密度理論計算 (DFT calculations) 進行研究,並進一步藉由 X-ray 電子光譜 (XPS) 和 X-ray 吸收近邊緣結構光譜 (XANES) 研究此系列聚合物的 Cu 金屬氧化態。 2. Se/Mn/CO 系統之研究 利用一鍋化反應將 Se 粉末與 Mn2(CO)10 以 5.4: 1 比例混合於 2 M KOH/MeOH/MeCN 溶液中於 90 oC 下反應,可成功得到一奇數電子之錳硒自由基團簇物 [Se5Mn3(CO)9]․2− (1)。化合物 1 可進一步藉由其雙聚化合物 [{Se5Mn3(CO)9}]4− (12) 以熱裂解的方式斷裂其中心之 Se−Se 鍵得之。反之,化合物 1 於高濃度的 MeCN 溶液中,亦可雙聚化形成 12,此反應暗示化合物 1 之 μ-Se 具有自由基的特性。具有自由基之化合物 1 可進一步利用含氧自由基試劑 TEMPO 進行捕捉,生成一以 TEMPO 穩定的化合物 [Se5Mn3(CO)9(TEMPO)]2− (2),並進一步由 ESI-MS 偵測。有趣的是,當化合物 1 與適當的雙鹵素氧化劑 CH2Cl2 和 Br(CH2)2Br 進行反應時,可得到一構型新穎之雙 CH2 引入及雙硒併入以 Se8Mn4 為基底之團簇物[{SeMn2(CO)6(Se2CH2Se)}2]2− (3) 和 [{SeMn2(CO)6(Se4)}2]2− (4)。經由 X-ray 構造解析可知,化合物 3 和 4 為同構結構 (isomorphous structures),3 和 4 皆可視為一具兩相同單體 Mn2(μ-η2,η2-Se2CH2Se)(μ-Se)(CO)6 或 Mn2(μ-η2,η2-Se4)(μ-Se)(CO)6 之雙聚物,並以兩個 μ-Se 原子以 μ4-η1,η1,η1,η1-Se22− 之鍵結模式串接形成的雙魚型 (double-fish) 結構,其對稱中心 (inversion center) 落在中心 Se−Se 之中點。經由 X-ray 電子光譜 (XPS)、電子順磁共振光譜 (EPR) 以及密度泛函理論計算 (DFT calculations) 結果顯示符合電子數的化合物 12、3 和 4 以及具有自由基之缺電子化合物 1 皆具有特殊的順磁性表現,此磁性表現是來自於兩種不同氧化態的錳金屬或硒自由基。此系列硒錳金屬團簇物具有豐富的氧化還原特性,並於固態下具有極低的能隙表現,此半導體特性係透過非典型的 C−H···O(carbonyl) 作用力進行有效的電子轉換。此系列化合物的結構特性、特殊的磁性表現、電子流通的骨架結構等特性皆利用 DFT 計算進行佐證。 3. Te/Mn/CO 系統之研究 藉由一鍋化合成可得到五個新穎的碲錳金屬羰基團簇化合物:螺環狀的 [Mn4Te(CO)16]2− (1)、Mn2Te2 四員環的 [Mn2Te2(CO)8]2− (2)、含氫配子之四角錐[HMn3Te2(CO)9]2− (3) 以及啞鈴型之 [Mn6Te6(CO)18]4− (4) 和 [Mn6Te10(CO)18]4− (5)。經由 X-ray 電子光譜 (XPS)、電子順磁共振光譜 (EPR) 以及密度泛函理論計算 (DFT calculations) 結果顯示符合電子數的化合物 4 和 5 具有特殊的順磁性表現,且此磁性表現是來自於兩種不同氧化態的錳金屬。經由可調控的結構轉換,少核數的 Mn4Te 1 和 Mn2Te2 2 可轉換至多核的 Mn6Te10 5、逆磁性的 HMn3Te2 3 可轉換至順磁性的 Mn6Te10 5 以及順磁性的 Mn6Te6 4 和 Mn6Te10 5 之間亦具有可逆的結構轉換。有趣的是,以 HMn3Te2 為基底之團簇物 3 可經由去氫配子化反應轉換成 [Mn3Te2(CO)9]−,並伴隨著高產率之氫氣生成。若將氫配子加成至 [Mn3Te2(CO)9]− 亦可逆反應生成 3。另一方面,將 3 加入 CO 可得一羰基引入之中間產物 [HMn3Te2(CO)10]2‒ (3ꞌ),將此中間物進一步加入 O2 可生成包含兩個氫配子的雙聚團簇物 [{HMn3Te2(CO)10}2]2‒ (6)。此系列少核至多核數的碲錳金屬羰基團簇物具有豐富的氧化還原特性,並於固態下具有極低的能隙表現 (1.06−1.62 eV),此半導體性質係透過非典型的 C−H···O(carbonyl) 作用力於團簇物骨架結構中進行有效的電子傳導。此系列化合物的可逆結構及磁性轉換關係、電子流通的骨架結構以及氫氣生成相關的化學特性皆利用 DFT 計算進行佐證。 4. E/Bi/Fe (E = Te, Se) 系統之研究 混合鉍−硫族−鐵之團簇物 [{EFe3(CO)9}Bi]− (E = Te, 1a; Se, 1b) 可藉由 [EFe3(CO)9]2− 於溫和條件下還原 BiCl3 得之。X-ray 晶體結構解析顯示,化合物 1a 和1b 具有金字塔型結構 (square-pyramidal geometry),其中裸露的鉍和硫族原子皆為扭曲的雙三角錐構型並伴隨一對具有立體活性的孤對電子對 (stereoactive lone pair)。為比較化合物 1a 和1b 中 6s/5s 和 6s/4s 孤對電子對之親核特性,1a 和 1b 進一步進行甲基化 (methylation) 及金屬化 (metalation) 反應。於金屬化反應中,化合物 1a 和 1b 上的鉍原子之 6s 電子對對於不飽和的 Cr(CO)5 具有特殊的親核特性,儘管化合物 1a 和 1b 同時具有化學活性較好之碲原子的 5s 電子對或硒原子的 4s 電子對。然而,於甲基化的反應中僅化合物 1b 中的硒原子的 4s 電子對可進行反應。若將化合物 1a 和1b 與適當的氧化劑 NaBiO3 或 K2SeO3 進行氧化反應,可得到一脫去化合物 1a 和 1b 中一 Fe(CO)3 頂點之混合鉍−硫族鍵結的四面體形化合物 [{EFe2(CO)6}Bi]− (E = Te, 4a; Se, 4b)。X-ray 電子光譜 (XPS)、X-ray 吸收近邊緣結構光譜 (XANES) 及理論計算結果皆顯示此系列化合物中的鉍原子之氧化態皆接近 +1 價。由於此帶正電性之鉍原子,化合物 1a (1b)、4a (4b) 以及金屬化的 3a (3b) 皆具有顯著的分子間及分子內 Bi···E 作用力,可生成由線性的 ···Bi···E···、Z字型的 ···Bi−E··· 或雙聚型的 Bi···E···E···Bi (E = Te, Se) 串接成的一維鏈狀結構。此鏈狀結構進一步藉由非典型 C−H···O(carbonyl) 連接並擴張成二維的骨幹結構。此分子間弱作用力可進一步利用理論計算進行佐證。此系列藉由帶正價數之鉍原子誘發的 Bi···E (E = Te, Se) 和羰基輔助的弱作用力,可有效的促進電子傳導於此二維的三元之鉍−硫族−鐵和四元之鉍−硫族−鐵−鉻團簇骨架中。此結果進一步反映於此系列化合物的半導體特性,其極低的能隙位於 1.01−1.21 eV 範圍內。
1. Se/Fe/Cu System A novel family of SeFe3(CO)9−dipyridyl hybrid two- and one-dimensional (2D and 1D) Cu(I) polymers have been synthesized viathe three-component liquid-assisted grinding (LAG) of [Cu(MeCN)4]+ and [SeFe3(CO)9]2− as well as rigid conjugated dipyridyls, 4,4’-dipyridyl (dpy) and 1,2-bis(4-pyridyl)ethylene (bpee), or flexible conjugation-interrupted dipyridyls, 1,2-bis(4-pyridyl)ethylane (bpea) and 1,3-bis(4-pyridyl)propane (bpp). These mechanochemical syntheses lead to formation of three different types of SeFe3(CO)9−dipyridyl hybrid Cu(I) polymers, namely, the SeFe3(CO)9−dipyridyl-linked 2D 5-fold interpenetrating polymer [(MeCN)(dpy)Cu(μ4-Se)Fe3(CO)9Cu(dpy)0.5]n (1-dpy-2D) and honeycomb-like polymer [(bpp)Cu(μ4-Se)Fe3(CO)9Cu(bpp)]n (1-bpp-2D), the SeFe3(CO)9-blocked, dipyridyl-connected, 1D zigzag chains [(μ3-Se)Fe3(CO)9Cu2(L)]n (L = bpee, 1-bpee-1D; bpea, 1-bpea-1D), and the SeFe3(CO)9-pendant, dpy-bridged, 1D zigzag-like polymer [(μ3-Se)Fe3(CO)9Cu(dpy)Cu(dpy)2]n (1-dpy-1D). Upon [SeFe3(CO)9]2−-Cu(I)- or dpy-induced LAG reactions, the rare reversible dimensionality transformation was achieved between 1-dpy-1D and 1-dpy-2D, which involved an unprecedentedly reversible non-interpenetrating/interpenetrating structural rearrangement. Similar strategy was applied successfully between 1D polymers, 1-bpee-1D and 1-bpea-1D, and their 2D polymeric derivatives, [(μ3-Se)Fe3(CO)9Cu(L)Cu(L)1.5]n (L = bpee, 1-bpee-2D; bpea, 1-bpea-2D), and between the di-cluster macrocycle [{(μ3-Se)Fe3(CO)9Cu2}2(bpp)2] and the 2D polymer, 1-bpp-2D. Notably, these synthesized polymers possessed extraordinary semiconducting characteristics with low but tunable energy gaps, especially low for the hybrid SeFe3(CO)9−conjugation-interrupted bpp-linked 1-bpp-2D that violated our knowledge, which was mainly attributed to the through-space electron transport via nonclassical C−H···O(carbonyl) hydrogen bonds between SeFe3(CO)9 and bpp, with significant aromatic C−H···π interactions between bpp caused by its closely packed 2D layers. With the low energy gaps, polymers 1-bpp-2D, 1-bpea-2D, and 1-dpy-1D were found to exhibit unique photodegradation activities, where 1-bpp-2D revealed the most pronounced performance toward the nitroaromatics and the organic dyes. In addition, polymers 1-dpy-2D, 1-bpp-2D, 1-bpea-2D, and 1-dpy-1D all possessed rare short-wavelength infrared emission properties. The intriguing structure–property relationships were also elucidated by X-ray analysis and DFT calculations and further demonstrated by a significant oxidation state change of the Cu atom by XPS and Cu K-edge XANES. 2. Se/Mn/CO System The odd-electron manganese carbonyl selenide radical cluster [Se5Mn3(CO)9]․2− (1) has been successfully synthesized from the one-pot reaction of Se powder and Mn2(CO)10 in a ratio of 5.4: 1 in 2 M KOH/MeOH/MeCN solutions at 90 oC. The mono-Se5Mn3-based cluster 1 could also be transformed from the di-Se5Mn3-based cluster [{Se5Mn3(CO)9}2]4− (12) via the thermal cracking process, accompanied by the central Se−Se bond breakage. Conversely, the radical anionic cluster 1 could further reconvert into its dimeric derivative 12 in concentrated MeCN solutions, implying that the radical character of the μ-Se in 1. Radical anionic cluster 1 could be trapped by the radical trapping reagent, (2,2,6,6-tetramethylpiperidin-1-yl)oxyl (TEMPO), leading to the formation of [Se5Mn3(CO)9(TEMPO)]2− (2), which was detected by ESI-MS. Upon the treatment with appropriate di-halide oxidizing reagents CH2Cl2 in refluxing condition or Br(CH2)2Br at 40 oC, 1 could produce two novel di-CH2-inserted or di-Se-incorporated Se8Mn4-based clusters, [{SeMn2(CO)6(Se2CH2Se)}2]2− (3) and [{SeMn2(CO)6(Se4)}2]2− (4), respectively. X-ray analysis showed that two Se8Mn4-based clusters 3 and 4 are isomorphous structures, which could be viewed as a dimeric structure possessing two identical monomeric Mn2(μ-η2,η2-Se2CH2Se)(μ-Se)(CO)6 or Mn2(μ-η2,η2-Se4)(μ-Se)(CO)6 moieties, respectively, linked together via two μ-Se with a μ4-η1,η1,η1,η1-Se22− bonding mode to give a double fish-like cluster, where an inversion center was located at the midpoint of the central Se−Se bond. These Se−Mn−CO complexes 12, 1, 3, and 4 exhibit unusual paramagnetism arising from two types of the Mn atoms in different oxidation states, as determined by X-ray photoelectron spectroscopy (XPS), electron paramagnetic resonance (EPR), and density functional theory (DFT) calculations. In addition, these high-nuclearity Se−Mn−CO complexes possess rich redox properties and semiconducting behaviors in solids with low but tunable energy gaps due to efficient electron transport via nonclassical C−H···O(carbonyl) interactions. The structural nature, unusual magnetic behaviors, and electron communication networks are discussed in detail and elucidated by DFT calculations, the density of states (DOS), band structures, and noncovalent interaction (NCI) analyses. 3. Te/Mn/CO System A novel family of five Mn −Te −CO complexes was prepared via facile syntheses: mono spirocyclic [Mn4Te(CO)16]2− (1), four-membered Mn2Te2 ring-type [Mn2Te2(CO)8]2− (2), hydride-containing square pyramidal [HMn3Te2(CO)9]2− (3), and dumbbell-shaped [Mn6Te6(CO)18]4− (4) and [Mn6Te10(CO)18]4− (5). Electron-precise complexes 4 and 5 exhibit unusual paramagnetism arising from two types of Mn atoms in different oxidation states, as determined by X-ray photoelectron spectroscopy, electron paramagnetic resonance, and density functional theory (DFT) calculations. The structural transformations from small-sized Mn4Te 1 and Mn2Te2 2 to the largest Mn6Te10 5 were controllable, the off/on magnetic-switched transformation between HMn3Te2 3 and 5 was reversible, and the magnetic transformation between Mn6Te6 4 and 5 was observed. Interestingly, the reversible dehydridation and hydridation between the HMn3Te2-based cluster 3 and [Mn3Te2(CO)9]− were successfully accomplished, in which the release of a high yield of H2 was detected by gas chromatography. In addition, upon the addition of CO, cluster 3 first forms a carbonyl-inserted intermediate [HMn3Te2(CO)10]2− (3'), detected by the high resolution ESI-MS, which is readily transformed to a dimeric dihydrido cluster [{HMn3Te2(CO)10}2]2− (6) with the introduction of O2. These low- to high-nuclearity complexes exhibit rich redox properties with semiconducting behavior in solids, possessing low but tunable energy gaps (1.06−1.62 eV) due to efficient electron transport via nonclassical C−H···O(carbonyl) interactions. The structural nature, reversible structural transformations, controllable on/off magnetic switches, electron communication networks, and associated chemical properties for hydrogen generation are discussed in detail and supported by DFT calculations, density of states, band structures, and noncovalent interaction analyses. 4. E/Bi/Fe (E = Te, Se) System Mixed bismuth−chalcogen−iron clusters [{EFe3(CO)9}Bi]− [E = Te (1a) or Se (1b)] were produced via the reduction of BiCl3 with [EFe3(CO)9]2− under mild conditions. X-ray analysis showed that both clusters 1a and 1b had a square-pyramidal geometry, where the naked Bi and chalcogen both adopted a distorted trigonal-pyramidal configuration with a stereoactive lone pair. Complexes 1a and 1b can be further functionalized by methylation and metalation, which permits the nucleophilicity of the 6s/5s and 6s/4s lone pairs to be compared. In the metalation, the 6s pair of the Bi atom in 1a and 1b had an extraordinary nucleophilicity toward the unsaturated Cr(CO)5 fragment, even in the presence of the more chemically active 5s or 4s pair, whereas in the case of methylation, only the 4s pair of Se could be selectively alkylated. Upon oxidation of 1a and 1b with suitable oxidizing agents, NaBiO3 or K2SeO3, Bi−E bonded tetrahedral complexes [{EFe2(CO)6}Bi]− [E = Te (4a) or Se (4b)] were formed by the elimination of one Fe(CO)3 vertex. X-ray photoelectron spectroscopy, X-ray absorption near-edge structure, and density functional theory (DFT) calculations showed that all of the Bi atoms in these complexes had oxidation states close to +1. Due to the electropositive character of the Bi atom, pronounced induced Bi···E inter- and intramolecular interactions were evident in 1a (1b), 4a (4b), and the metalated 3a (3b), where their linear-like ···Bi···E··· or zigzag-like ···Bi−E··· (E = Te or Se) chain or the Bi···E···E···Bi (E = Te or Se) dimeric chain can further expand into the two-dimensional network via nonclassical C−H···O(carbonyl) interactions, supported by noncovalent interaction index and DFT calculations. These positively charged Bi-induced Bi···E (E = Te or Se) and carbonyl-aided weak interactions can facilitate efficient electron transport within these ternary Bi−E−Fe or quaternary Bi−E−Fe−Cr cluster-based frameworks, resulting in semiconducting behavior with surprising ultranarrow energy gaps of 1.01−1.21 eV.
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