MoV2O42+ Directs the Formation and Subsequent Linking of Potential Building Blocks under Different Boundary Conditions: A Related Set of Novel Cyclic Polyoxomolybdates

Abstract

Keywords: Molybdenum / Polyoxometalates / Clusters / Ring structuresThe synthesis and structural characterization of a novel series of deep-red mixed-valence (Mo VI /Mo V ) compounds with nano-sized spherically shaped cluster anions containing 18, 40, or 54 Mo atoms, respectively, is reported: Na 10 -[H 4 Mo 18 O 56 (CH 3 COO) 2 ] × ca. 36 H 2 O × 3 CH 3 COOH (1), (NH 4 ) 12 Na 12 [Mo 40 O 128 ] × ca. 70 H 2 O (2), (NH 4 ) 12 Na 20 [H 4-Mo 54 O 168 (CH 3 COO) 4 ] × ca. 64 H 2 O (3), Na 32 [H 4-Mo 54 O 168 (CH 3 COO) 4 ] × ca. 128 H 2 O (4), and Na 32 [H 4-Mo 54 O 168 (CH 3 COO) 4 ] × ca. 98 H 2 O (5). Clusters 3, 4, and 5 [a]

A novel hybrid crystal of chiral racemic complexes coexisting with two kinds of polyoxomolybdates: synthesis and structure of [Co(bpy)3]2[Mo6O19] [β-(H2Mo8O26)]·4H2O

“…The +6 oxidation state of molybdenum in 1 is consistent with the bond valance sum (BVS ave ¼ 5.94) [9]. According to the results of the bond valance sum for all oxygen atoms in b-[Mo 8 anion should be considered to be a type-III system because of the coexistence of both sorts of octahedra. Another interesting aspect of 1 is that Co(bipy) 3 complex parts appear in racemic enantiomorphous pair architecture.…”

“…To rationally design and control the structures of the POM-organic hybrids, it is of great importance to establish the structural stabilities and convertibilities of these POM anions in aqueous solution. A lot of previous research literature provided various spectral and electrochemical data to elucidate the structural stabilities and convertibilities mechanism of [Mo 6 [7,8]. Our result further suggests that by keeping an appropriate range of pH value, two or more kinds of POM anions may stably coexist in the solution, so that a crystal structure of the coexistence phase can form under rational reaction condition.…”

A novel hybrid crystal of chiral racemic complexes coexisting with two kinds of polyoxomolybdates: synthesis and structure of [Co(bpy)3]2[Mo6O19] [β-(H2Mo8O26)]·4H2O

“…The +6 oxidation state of molybdenum in 1 is consistent with the bond valance sum (BVS ave ¼ 5.94) [9]. According to the results of the bond valance sum for all oxygen atoms in b-[Mo 8 anion should be considered to be a type-III system because of the coexistence of both sorts of octahedra. Another interesting aspect of 1 is that Co(bipy) 3 complex parts appear in racemic enantiomorphous pair architecture.…”

“…To rationally design and control the structures of the POM-organic hybrids, it is of great importance to establish the structural stabilities and convertibilities of these POM anions in aqueous solution. A lot of previous research literature provided various spectral and electrochemical data to elucidate the structural stabilities and convertibilities mechanism of [Mo 6 [7,8]. Our result further suggests that by keeping an appropriate range of pH value, two or more kinds of POM anions may stably coexist in the solution, so that a crystal structure of the coexistence phase can form under rational reaction condition.…”

Spontaneous self-assembly of a giant spherical metal-oxide Keplerate: addition of one building block induces “immediate” formation of the complementary one from a constitutional dynamic library

“…It was soon assumed that the [Mo V ]/[Mo VI ] ratio and the pH are crucial for the formation of 1a 13 and that the {Mo V 2 O 4 } 2+ groups may play a key role in different scenarios for the formation and subsequent linking of various building blocks under different boundary conditions. 15 In a similar way it has been recently found that {Mo V 2 O 2 S 2 } 2+ groups allow to trap a new isomer of the [Mo 8 O 26 ] 4À ion from an acidified aqueous solution of molybdate. 16 Now we were interested to investigate whether the addition of the preformed {Mo V 2 O 4 } 2+ unit/building block to an aqueous solution of molybdate (practically identical to the published method leading to 1 13,14 ) would result in the spontaneous formation of 1a based on the fast formation of the mentioned pentagonal building blocks (Scheme 1).…”

Wheel-shaped polyoxometalates as nanozymes for autophagy-augmented and phototherapy-involved cancer nanotherapy

“…A series of mixed-valence compounds featuring nano-sized spherical cluster anions composed of 18, 40, or 54 Mo atoms were synthesized using a method outlined earlier [ 2 ], where these nanoagents were efficiently generated via the reduction of an acidified aqueous molybdate solution, with the appearance as shown in Fig. S1 and the crystallographic information listed in Table S1 [ 2 ]. The preparation methods are presented in the Supplementary data.…”

A novel hybrid crystal of chiral racemic complexes coexisting with two kinds of polyoxomolybdates: synthesis and structure of [Co(bpy)3]2[Mo6O19] [β-(H2Mo8O26)]·4H2O

“…The +6 oxidation state of molybdenum in 1 is consistent with the bond valance sum (BVS ave ¼ 5.94) [9]. According to the results of the bond valance sum for all oxygen atoms in b-[Mo 8 anion should be considered to be a type-III system because of the coexistence of both sorts of octahedra. Another interesting aspect of 1 is that Co(bipy) 3 complex parts appear in racemic enantiomorphous pair architecture.…”

“…To rationally design and control the structures of the POM-organic hybrids, it is of great importance to establish the structural stabilities and convertibilities of these POM anions in aqueous solution. A lot of previous research literature provided various spectral and electrochemical data to elucidate the structural stabilities and convertibilities mechanism of [Mo 6 [7,8]. Our result further suggests that by keeping an appropriate range of pH value, two or more kinds of POM anions may stably coexist in the solution, so that a crystal structure of the coexistence phase can form under rational reaction condition.…”

Spontaneous self-assembly of a giant spherical metal-oxide Keplerate: addition of one building block induces “immediate” formation of the complementary one from a constitutional dynamic library

“…It was soon assumed that the [Mo V ]/[Mo VI ] ratio and the pH are crucial for the formation of 1a 13 and that the {Mo V 2 O 4 } 2+ groups may play a key role in different scenarios for the formation and subsequent linking of various building blocks under different boundary conditions. 15 In a similar way it has been recently found that {Mo V 2 O 2 S 2 } 2+ groups allow to trap a new isomer of the [Mo 8 O 26 ] 4À ion from an acidified aqueous solution of molybdate. 16 Now we were interested to investigate whether the addition of the preformed {Mo V 2 O 4 } 2+ unit/building block to an aqueous solution of molybdate (practically identical to the published method leading to 1 13,14 ) would result in the spontaneous formation of 1a based on the fast formation of the mentioned pentagonal building blocks (Scheme 1).…”

Wheel-shaped polyoxometalates as nanozymes for autophagy-augmented and phototherapy-involved cancer nanotherapy

“…A series of mixed-valence compounds featuring nano-sized spherical cluster anions composed of 18, 40, or 54 Mo atoms were synthesized using a method outlined earlier [ 2 ], where these nanoagents were efficiently generated via the reduction of an acidified aqueous molybdate solution, with the appearance as shown in Fig. S1 and the crystallographic information listed in Table S1 [ 2 ]. The preparation methods are presented in the Supplementary data.…”

A novel hybrid crystal of chiral racemic complexes coexisting with two kinds of polyoxomolybdates: synthesis and structure of [Co(bpy)3]2[Mo6O19] [β-(H2Mo8O26)]·4H2O

“…The +6 oxidation state of molybdenum in 1 is consistent with the bond valance sum (BVS ave ¼ 5.94) [9]. According to the results of the bond valance sum for all oxygen atoms in b-[Mo 8 anion should be considered to be a type-III system because of the coexistence of both sorts of octahedra. Another interesting aspect of 1 is that Co(bipy) 3 complex parts appear in racemic enantiomorphous pair architecture.…”

“…To rationally design and control the structures of the POM-organic hybrids, it is of great importance to establish the structural stabilities and convertibilities of these POM anions in aqueous solution. A lot of previous research literature provided various spectral and electrochemical data to elucidate the structural stabilities and convertibilities mechanism of [Mo 6 [7,8]. Our result further suggests that by keeping an appropriate range of pH value, two or more kinds of POM anions may stably coexist in the solution, so that a crystal structure of the coexistence phase can form under rational reaction condition.…”

Spontaneous self-assembly of a giant spherical metal-oxide Keplerate: addition of one building block induces “immediate” formation of the complementary one from a constitutional dynamic library

“…It was soon assumed that the [Mo V ]/[Mo VI ] ratio and the pH are crucial for the formation of 1a 13 and that the {Mo V 2 O 4 } 2+ groups may play a key role in different scenarios for the formation and subsequent linking of various building blocks under different boundary conditions. 15 In a similar way it has been recently found that {Mo V 2 O 2 S 2 } 2+ groups allow to trap a new isomer of the [Mo 8 O 26 ] 4À ion from an acidified aqueous solution of molybdate. 16 Now we were interested to investigate whether the addition of the preformed {Mo V 2 O 4 } 2+ unit/building block to an aqueous solution of molybdate (practically identical to the published method leading to 1 13,14 ) would result in the spontaneous formation of 1a based on the fast formation of the mentioned pentagonal building blocks (Scheme 1).…”

Wheel-shaped polyoxometalates as nanozymes for autophagy-augmented and phototherapy-involved cancer nanotherapy

“…A series of mixed-valence compounds featuring nano-sized spherical cluster anions composed of 18, 40, or 54 Mo atoms were synthesized using a method outlined earlier [ 2 ], where these nanoagents were efficiently generated via the reduction of an acidified aqueous molybdate solution, with the appearance as shown in Fig. S1 and the crystallographic information listed in Table S1 [ 2 ]. The preparation methods are presented in the Supplementary data.…”