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Rapid and Simple Isolation of the Crystalline Molybdenum‐Blue Compounds with Discrete and Linked Nanosized Ring‐Shaped Anions: Na 15 [Mo {126} {VI} Mo {28} V O 462 H 14 (H 2 O) 70 ] 0.5 [Mo {124} {VI} Mo {28} V O 457 H 14 (H 2 O) 68 ] 0.5 · ca. 400 H 2 O and Na 22 [Mo {118} {VI} Mo {28} V O 442 H 14 (H 2 O) 58 ] · ca. 250 H 2 O
Author(s) -
Müller Achim,
Das Samar K.,
Fedin Vladimir P.,
Krickemeyer Erich,
Beugholt Christian,
Bögge Hartmut,
Schmidtmann Marc,
Hauptfleisch Björn
Publication year - 1999
Publication title -
zeitschrift für anorganische und allgemeine chemie
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.354
H-Index - 66
eISSN - 1521-3749
pISSN - 0044-2313
DOI - 10.1002/(sici)1521-3749(199907)625:7<1187::aid-zaac1187>3.0.co;2-#
Subject(s) - molybdenum , ring (chemistry) , materials science , inorganic chemistry , simple (philosophy) , crystallography , nanotechnology , chemistry , organic chemistry , philosophy , epistemology
The blue mixed‐crystal title compound Na 15 [Mo {126} {VI} Mo {28} V O 462 H 14 (H 2 O) 70 ] 0.5 [Mo {124} {VI} Mo {28} V O 457 H 14 · (H 2 O) 68 ] 0.5 · ca. 400 H 2 O ≡ Na 15 [ 1 a ] 0.5 [ 1 b ] 0.5 · ca. 400 H 2 O 1 , which crystallizes in the triclinic space group P 1 (a = 30.785(2), b = 32.958(2), c = 47.318(3) Å, α = 90.53(1), β = 89.86(1), γ = 96.85(1)°, V = 47665(6) Å 3 , Z = 2, D calc = 2.149 g cm –3 ), precipitates within one day when an acidic (pH ≈ 1) aqueous solution of sodium molybdate (because of the extremely high solubility of the reaction product used in relatively high concentration) is reduced by sodium dithionite. 1 contains hitherto unknown pure molybdenum‐oxide based, nanosized, ring‐shaped, crystallographically independent cluster anions of the type {Mo 154 } 1 a and {Mo 152 } 1 b , the lacunary‐type analogue of 1 a . Using the same reducing agent but in the presence of a reagent with a high affinity to the specific {Mo 2 }‐type building unit (also a leaving group) of 1 a , such as formic acid, the compound Na 22 [Mo {118} {VI} Mo {28} V O 442 H 14 (H 2 O) 58 ] · ca. 250 H 2 O 2 (space group P 1, a = 24.724(1), b = 35.726(2), c = 44.608(3) Å, α = 93.25(1), β = 93.51(1), γ = 106.72(1)°, V = 37552(4) Å 3 , Z = 2, D calc = 2.401 g cm –3 ) is obtained in which the giant rings, having four missing {Mo 2 } units compared to 1 a , are linked to chains. Until now, similar chain‐type compounds could only be obtained using a non‐well‐defined synthetic method.