Horwitz N.E., Xie J., Filatov A.S. et al. · Journal of the American Chemical Society · 2019 · 3940-3951
Open a family to keep every result attached to its sample, method and conditions.
Paraphrased for this database from the authors’ stated interpretations — never quoted verbatim — and kept separate from reported measurements.
Compounds 1 and 2 are crystalline 1D coordination polymers made from Fe4S4 clusters linked by pairs of BDT ligands.
Caveat: Structures are solved from synchrotron powder diffraction rather than single-crystal data.
3942 · Structural Determination · Figures 2 and 3 · Linked to 4 structured results
The Fe4S4-BDT chain structure of 2 persists in DMF solution and after partial solution reduction.
Caveat: SAXS and spectroscopy support polymer persistence but do not provide an atomistic solution structure.
3943, 3945 · Solution Behavior; Electronic Properties · Figures 4, S24, S25, S41, S42 · Linked to 3 structured results
The countercation changes chain packing, conformation, and solubility: TBA separates chains in 1, while smaller TMA gives closer chain contacts and DMF solubility for 2.
Caveat: The role of ionic strength is proposed from precipitation and SAXS observations rather than direct mechanistic proof.
3943 · Solution Behavior · Figure 4; Figure S47 · Linked to 4 structured results
The Fe4S4 cluster redox activity is retained in the Fe4S4-BDT chains.
Caveat: CV of 2 depends on counterion/electrolyte and can involve precipitation/deposition.
3944 · Electronic Properties · Figure 6; Figures S33-S38 · Linked to 3 structured results
The low pristine pressed-pellet conductivity is attributed to low charge-carrier concentration in S = 0 [Fe4S4]2+ chains and to bulk pellet averaging over crystallographic directions plus grain-boundary resistance.
Caveat: Mechanistic explanation is proposed, not directly separated into intrinsic and grain-boundary contributions.
3944 · Electronic Properties · Linked to 4 structured results
Introducing charge carriers by reducing Fe4S4 clusters increases electrical conductivity, most strongly for compound 2.
Caveat: Pressed-pellet measurements include grain-boundary and anisotropy effects; the highest conductivity is from an amorphous reprecipitated sample.
3944-3945 · Electronic Properties · Table 1 · Linked to 5 structured results
Names and aliases are kept exactly within the paper’s own identity model.
| Material | Composition | Structure context | Source |
|---|---|---|---|
| [Fe4S4(BDT)2][TBA]2, compound 1 | C44H80Fe4N2S8; Fe4S4(C6H4S2)2.2N(C4H9)4Cubane Fe4S4 clusters · 1,4-benzenedithiolate (BDT) | 1D · PristineTetragonal P 42 c m (#101); chains of Fe4S4 clusters connected by pairs of BDT groups and separated by TBA cations. | 3941-3942 · Results and Discussion - Synthesis and Composition; Structural Determination · Figures 2; Table S2 |
| [Fe4S4(BDT)2][TMA]2, compound 2 | C20H32Fe4N2S8; Fe4S4(C6H4S2)2.2N(CH3)4Cubane Fe4S4 clusters · 1,4-benzenedithiolate (BDT) | 1D · PristineTetragonal I 41/a (#88:2); Fe4S4-BDT chains with two alternating Fe4S4 sites and TMA cations in channels. | 3941-3942 · Results and Discussion - Synthesis and Composition; Structural Determination · Figures 3; Table S3 |
| [Fe4S4(SPh)4][TBA]2 | [Fe4S4(SPh)4][TBA]2Molecular Fe4S4 thiophenolate cluster · Thiophenolate, not polymeric | 0D · Model SystemMolecular precursor/control, not a coordination polymer. | 3941, 3944 · Synthesis and Composition; Electronic Properties |
| [Fe4S4(SPh)4][TMA]2 | [Fe4S4(SPh)4][TMA]2Molecular Fe4S4 thiophenolate cluster · Thiophenolate, not polymeric | 0D · Model SystemMolecular precursor/control, not a coordination polymer. | 3946 · Experimental Section - Synthetic Procedures |
Sample form, processing state and composition status define the context for measurements.
| Sample | Form and role | Processing and geometry | Source |
|---|---|---|---|
| Compound 1 as-synthesized black powderresearch_0467__mat__mat_1_tba_fe4s4_bdt | Powder · Target Sample · Pristine Framework | As-synthesized powder; for conductivity pressed into pellets under N2. | 3946 · Experimental Section - [Fe4S4(BDT)2][TBA]2 (1) |
| Compound 1 oxidatively treated solidresearch_0467__mat__mat_1_tba_fe4s4_bdt | Powder · Target Sample · Doped | Solid 1 treated overnight with [Fc][BF4] and excess [TMA][Br] in MeCN/MeOH. | 3944, 3946 · Electronic Properties; Experimental Section - Oxidative Doping Experiments · Figure S16 |
| Compound 1 after [TBA][PF6] treatmentresearch_0467__mat__mat_1_tba_fe4s4_bdt | Powder · Target Sample · Pristine Framework | 1 treated with [TBA][PF6] in DMF/MeCN at 100 C, then washed and dried. | 3946 · Experimental Section - Treatment with [R4N][PF6] · Table S1; Figure S13 |
| Compound 1 reductively doped solidresearch_0467__mat__mat_1_tba_fe4s4_bdt | Powder · Target Sample · Doped | Solid 1 soaked overnight in THF with CoCp*2 and excess LiCF3SO3; washed and dried. | 3944, 3946 · Electronic Properties; Experimental Section - Reductive Doping Experiments · Figure S15; Table 1 |
| Compound 2 as-synthesized black powderresearch_0467__mat__mat_2_tma_fe4s4_bdt | Powder · Target Sample · Pristine Framework | As-synthesized powder; for conductivity pressed into pellets under N2. | 3946 · Experimental Section - [Fe4S4(BDT)2][TMA]2 (2) |
| Compound 2 in DMF solutionresearch_0467__mat__mat_2_tma_fe4s4_bdt | Unknown · Target Sample · Pristine Framework | Near-saturated or analytical DMF solution of 2 used for SAXS, UV-visible, and CV. | 3943, 3947 · Solution Behavior; Small Angle X-ray Scattering · Figures 4-6 |
| Compound 2 oxidatively treated solidresearch_0467__mat__mat_2_tma_fe4s4_bdt | Powder · Target Sample · Doped | Solid 2 treated overnight with [Fc][BF4] and excess [TMA][Br] in MeCN/MeOH. | 3944, 3946 · Electronic Properties; Experimental Section - Oxidative Doping Experiments · Figure S18 |
| Compound 2 after [TMA][PF6] treatmentresearch_0467__mat__mat_2_tma_fe4s4_bdt | Powder · Target Sample · Pristine Framework | 2 treated with [TMA][PF6] in DMF/MeCN at 100 C, then washed and dried. | 3946 · Experimental Section - Treatment with [R4N][PF6] · Table S1; Figure S14 |
| Compound 2 reductively doped solidresearch_0467__mat__mat_2_tma_fe4s4_bdt | Powder · Target Sample · Doped | Solid 2 soaked overnight in THF with CoCp*2 and excess LiCF3SO3; washed and dried. | 3944, 3946 · Electronic Properties; Experimental Section - Reductive Doping Experiments · Figure S17; Table 1 |
| 2 precipitated from DMF solution without reductantresearch_0467__mat__mat_2_tma_fe4s4_bdt | Powder · Pristine Control · Pristine Framework | Material precipitated from DMF solution of 2 without added reductant. | 3945 · Electronic Properties |
| Partially reduced 2 precipitated from DMF solutionresearch_0467__mat__mat_2_tma_fe4s4_bdt | Powder · Target Sample · Doped | DMF solution of 2 treated with about 0.5 equiv sodium acenaphthylene, then precipitated with Et2O; amorphous solid. | 3945, 3946 · Electronic Properties; Experimental Section - Chemical Reduction of 2 in Solution · Figures S24, S25, S27, S41, S42 |
| [Fe4S4(SPh)4][TBA]2 precursor controlresearch_0467__mat__mat_tba_monomer_control | Powder · Model System · Model | Molecular precursor measured as conductivity comparison. | 3944 · Electronic Properties |
| [Fe4S4(SPh)4][TMA]2 precursor controlresearch_0467__mat__mat_tma_monomer_control | Powder · Model System · Model | Molecular precursor measured as conductivity and electrochemistry comparison. | 3944 · Electronic Properties · Figure S43 |