Directing the Structure of Metal–Organic Frameworks by Oriented Surface Growth on an Organic Monolayer

Abstract

Orientierung und Struktur poröser metall‐organischer Gerüste (MOFs) aus Eisen und 1,4‐Benzoldicarbonsäure können durch heterogene Keimbildung auf selbstorganisierten Monoschichten aus Sulfanylhexadecansäure (MHDA) beeinflusst werden. Bei homogener Keimbildung entsteht das MOF Fe‐MIL‐53, während in der gleichen Kristallisationslösung auf einer MHDA‐funktionalisierten Goldoberfläche ausgerichtetes Fe‐MIL‐88B wächst (siehe Bild).

“Breathing” in Adsorbate‐Responsive Metal Tetraphosphonate Hybrid Materials

“…[4] Whether this field is perceived as a curiosity-driven or applications-driven field, it is broadly accepted that it has significantly taken the level of inorganic/materials chemistry forward. [5] There are now thousands of papers published every year on (functional) coordination polymers (with an emphasis on the porous family members) with potential applications including metal-ion sorption, [6] ion exchange, [7] gas absorption and storage (H 2 , [8] CO 2 , [9] CH 4 , [10] and others [11] ), catalysis, [12] fuel cells, [13] surface chemistry, [14] magnetism, [15] and separation. [16] Among the exciting properties of these (porous) coordination polymers, the "breathing effect" has captured the attention of a number of research groups; [17] it can be described as dramatic changes in the dimensions of a stable framework (e.g., unit-cell dimensions) caused by an external stimulus (molecules added and stored within the framework).…”

Growth Mechanism of Metal–Organic Frameworks: Insights into the Nucleation by Employing a Step‐by‐Step Route

“…In their studies, organothiol-based COOH-terminated and OH-terminated SAMs were immersed at room temperature into an aged (8 days) and filtered mother solution for the solvothermal synthesis of HKUST-1 and MIL-88b. [27,28] This template-effect of the organic surface can be rationalized by inspection of the bulk structure of [Cu 3 (btc) 2 ] (Figure 2 2 ] will lead to the formation of copper-carboxylate bonds just as in the bulk phase. Differently oriented [Cu 3 (btc) 2 ] surfaces will contain both carboxylate-binding and Cu 2+ -binding units, and therefore the interaction energy with a COOH-terminated surface will be substantially smaller.…”

Wachstumsmechanismen Metall‐organischer Gerüststrukturen: Einblicke in die Keimbildung anhand einer schrittweisen Methodik

“…Substrate mit COOH-und OH-terminierten Organothiol-SAMs wurden bei Raumtemperatur in eine acht Tage gealterte und filtrierte Mutterlösung der Solvothermalsynthese von HKUST-1 und MIL-88b getaucht. [27,28] Dieser Templateffekt der organischen Oberfläche lässt sich anhand der Volumenstruktur von [Cu 3 …”